MOLTEN SALTS IONIC LIQUIDS BULLETIN M. GAUNE-ESCARD Editor 2013 – N° 108 EDITORIAL Molten Salts : what is still needed? Patrick J. Masset1 Fraunhofer UMSICHT, Institute Branch Sulzbach-Rosenberg Germany Molten salts are versatile liquids which are used in numerous industrial processes due to their special physico-chemical properties. Most molten salts exhibit high degrees of ionicity, close to 100% in the liquid state. It makes them suitable for use as electrolyte in industrial processes, as they exhibit high ionic conductivities (a few to tens of S.cm-1), almost negligible electronic conductivity associated with a rather good thermal stability, and to some extend a good resistance to radiation. Currently, molten salts are used or planned to be used in several industrial processes: - power generation: molten carbonate fuel cells (MCFC), thermal batteries - electrolytic processes for metal production: aluminum, sodium - energy transport/storage: solar system, phase change material (PCMs) - reprocessing: nuclear spent fuels (pyrochemistry), electronic scraps - coating production: electrodeposition of reactive metals Depending on their composition, molten salts’ melting temperatures range between 100 °C for nitrate-based molten salts and up to 1000°C for fluoride-based molten salts. The combination of suitable cations and anions gives the possibility to select 1 Head of Department “New Materials”, Fraunhofer UMSICHT, Institute Branch Sulzbach-Rosenberg,An der Maxhütte 1, D-92237 Sulzbach-Rosenberg, Germany Contact: Patrick.masset@umsicht.fraunhofer.de MOLTEN SALTS & IONIC LIQUIDS N° 108 page 1 EDITORIAL mixtures with a specific melting temperature range to enhance certain specific physico-chemical properties. However, it should be mentioned that there are no clear trends which provide a direct correlation between molten salts’ composition and their physico-chemical properties. Indeed, due partially to the difficulty of performing experiments at high temperatures, the properties of molten salts are less investigated and understood. Currently, there is a need to combine theoretical modeling with experimental data harvesting to obtain a better understanding of the relationship between the local structure of molten salt and its physico-chemical properties. As illustrated, the solvation structure of cations in molten salts depends on the composition of the molten salt, which modifies strongly the cation’s oxidation state and possible clustering. Ions should not be considered as rigid ions with a localized charge but rather as a polarisable species able to share its charge depending on its environment and surrounding species. This gives rise to the development of new theoretical models based on Density Functional Theory which takes into account the polarisabilty of the species in the salt. Experimental investigations using techniques such as EXAFS, X-ray and neutron scattering should provide suitable data to test the accuracy of the models. Detailed computer simulations and modeling will provide new insights on the effect of the composition on the local structure. This could be conducive to obtaining a deeper understanding of phenomena such oxo-, fluoro- and chloro-acidity, which play a crucial role in electrolysis processes and corrosion issues. The predictions of the new models should become the basis for the determination of further thermo-chemical properties such as surface tension, diffusivity, thermal and ionic conductivity, viscosity… using the “energy information” contained in the models. However, the impact of impurities in real molten salts represents a major challenge, as unknown (but low) concentrations of impurities can affect the quality of page 2 MOLTEN SALTS & IONIC LIQUIDS N° 108 EDITORIAL experimental results, and so the quality of tests of theoretical predictions against experiment. New techniques will need to be developed to control issues such as corrosion and reactivity of molten salts with the container. As an alternative, containerless technique such as reactive/inert gas levitation may be employed. A predictive model, supported by experiments, will be able to provide valuable data to process modeling (fluid mechanics, heat transfer…), for the material selection (infiltration and/or corrosion issues) and the determination of process parameters (production purity, current, voltage…). This short introduction invites new generations to use modern computational capabilities and large facilities to obtain a deeper insight on the structure and properties of molten salts to be used in industrial processes. This is a combined approach using theoretical models and experimental investigations. In addition, interdisciplinary collaboration becomes a key principle in combining skills in mathematical modeling, chemistry and materials science. As this approach covers a large spectrum of competencies, collaborative work between research groups is required, with the main challenge being the ability to speak the same language. Finally, it can be said that the term “multiscale modeling” summarizes quite well this approach, as it starts from the modeling/investigation of the local structure of the molten salt up to its macroscopic thermochemical and thermophysical properties. This represents a considerable step forward as it rationalises the use of the computational and experimental resources to derive some predictive tools that can be used to adjust compositions to design molten salts of specific physico-chemical properties. MOLTEN SALTS & IONIC LIQUIDS N° 108 page 3 CONFERENCE REPORTS Symposium VV: Materials Applications of Ionic Liquids 2013 MRS Spring Meeting & Exhibit April 1-5, 2013 • San Francisco, California (USA) Symposium Organizers Rico E. Del Sesto, Sheng Dai, Robin D. Rogers, Yukihiro Yoshida VV1 Chairs: Rico E. Del Sesto, Charles Hussey Electrochemistry and Spectroscopy of f-Electron Elements in Room-temperature Ionic Liquids Charles L. Hussey, Li-Hsien Chou, Yunfeng Pan Nanoparticle Electrides Scott C Warren, Yong Yan, Bartosz Grzybowski CO2 Reactive Ionic Liquids Prepared from Novel Substituted-Triazoles Robert L. Thompson, Hunaid Nulwala, Erik Albenze, Damodaran Krishnan, David Luebke. Novel Collection, Storage, and Analysis of CBRNE Forensic Samples Using Ionic Liquids John S. Wilkes, Cynthia Corley, Jessica Drewicz, Michelle Kiyota, Joseph A. Levisky, Hannah A. Miller, Michael Wilcox Structure-property Relations in Ionic Liquid Crystals Anja V Mudring, Kathrin Stappert, Mei Yang Acid Catalyzed Hydrolysis of Biomass in Ionic Liquid and Separation of Sugars Using Liquid-liquid Extraction Ning Sun, Noppadon Sathitsuksanoh, Kim Tran , Vitalie Stavila, Anthe George, Kenneth L Sale , Seema Singh , Blake A Simmons , Bradley M Holmes Electrowetting-on-Dielectric Behavior of Ionic Liquids: Fluidic versus Electrical Hysteresis Effects Natalie Gogotsi, Marriner Merrill, James P. Thomas Selective Gas Absorption by Ionic Liquids and by Supported Ionic Liquid-phase (SILP) Absorbers - Mechanistic Aspects Rasmus Fehrmann, Andreas J. Kunov-Kruse, Peter Thomassen, Susanne L. Mossin, Helene Kolding, Anders Riisager, Saravanamurugan Shunmugavel, Jacques Rogez. ___________________________________________________________________________ page 4 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS VV2 Chairs: Sheng Dai, Toshio Sumida Recent Progress in KOEI’s Ionic Liquid Toshio Sumida, Mayumi Nishida Inkjet Printing of Ionic Liquids for the Formation of Surface Structures on Biopolymer Substrates Kurt D Sweely, Luke M. Haverhals, Matthew P. Foley, Eva K. Brown, Hugh C. De Long, Paul C. Trulove Electrospinning of Biopolymers from Ionic Liquid Co-solvent Systems Eva Kathryn Brown, Luke M. Haverhals, Kurt D. Sweely, Matthew P. Foley, Hugh C. De Long, Paul C. Trulove Deep Eutectic Solvents Playing Multiple Roles in the Synthesis of Hierarchical Monolithic Carbons Francisco del Monte, Maria C. Gutierrez, Julian Patino, Elena Posada, M. Nieves Lopez-Salas, Daniel Carriazo, M. Luisa Ferrer Carbon Dioxide Capture and Electro-reduction in Imidazolium Ionic Liquids at Metal Electrodes John D. Watkins, Andrew B Bocarsly Development of Advanced Liquid Composite Materials by Controlling Stabilization of Nanoparticles in Ionic Liquids Robin D Rogers, Parker D McCrary Microscopic Insights of Ionic Liquids in Gas Separations and Energy Storage De-en Jiang VV3: Poster Session Chairs: Rico E. Del Sesto, Yukihiro Yoshida Electroposition in Ionic Liquid of SiGe Alloy Thin Films and Nanowires Karine Namur, Jeremy Mallet, Florie Martineau, Michel Troyon, Michael Molinari Supramolecular Features of Materials Based on Zwitterionic Molecules: A Quantum Chemical Study Ernesto Lopez-Chavez, Alberto Garcia-Quiroz, Gabriela Esmeralda Orozco___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 5 CONFERENCE REPORTS Duran, Luis Silvestre Zamudio-Rivera, Jose Manuel Martinez-Magadan, Eduardo Buenrostro-Gonzalez, Raul Hernandez-Altamirano. Glyme-Na Salt Complex as a New Solvate Ionic Liquid Shoshi Terada, Risa Nozawa, Kazuki Yoshida, Kaoru Dokko, Masayoshi Watanabe, Kazuhide Ueno Pyrrolinium-based Ionic Liquids with Ether Substituents as Electrolytes for Lithium Ion Batteries Hyung-Tae Kim, Hyeroung Lee, Oh min Kwon, Taeeun Yim, Junyoung Mun, Seung M. Oh, Geon Joong Kim, Young Gyu Kim Polymeric Ionic Liquids with Enhanced Electrical Conductivity and Tuneable Mechanical Properties Kaija Pohako-Esko, Martin Timusk , Silver Leinberg, Kristjan Saal, Ruenno Lohmus, Ilmar Kink, Uno Maeorg Lithium Solvate Ionic Liquids for Polymer Electrolytes Ryosuke Kido, Kaori Iwata, Satoru Imaizumi, Kazuhide Ueno, Kaoru Dokko, Masayoshi Watanabe High Performance Ionic Liquid Based Electrolytes for Energy Applications Frank M Stiemke, Thomas J.S. Schubert, Maria Ahrens. Development of High-current Ionic Liquid Ion Source toward Surface Modification Mitsuaki Takeuchi, Takuya Hamaguchi, Hiromichi Ryuto, Gikan H Takaoka VV4 Chairs: De-en Jiang, Frank Endres Confined Ionic Liquids within Host Networks: From Intensive ILs Properties to Solid Devices Aurelie Guyomard-Lack, Pierre-Emmanuel Delannoy, Jean Le Bideau. Electroposition in Ionic Liquid of Si and Ge Related Nanowires (NWs) and Nanotubes (NTs) Jeremy Mallet, Karine Namur, Florie Martineau, Michel Troyon, Michael Molinari (Functional) Coatings by Metal Deposition from Ionic Liquids Frank M Stiemke, Thomas J.S. Schubert, Maria Ahrens, Sven Sauer ___________________________________________________________________________ page 6 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Morphologies and Ionic Conductivity in Polymerized Ionic Liquid Block Copolymers Sharon Wang, Yuesheng Ye, Jae-Hong Choi, Yossef A. Elabd, Karen I. Winey Electrolyte-gated Transistors Based on Light-emitting Solution-processable Films Jonathan J. Sayago, Yuvaraj Sivalingam, Mitesh Patel, Fabio Cicoira New Ionic Liquid Gels and Their Application in ZnO Field-effect Transistors Stefan Thiemann, Swetlana Sachnov, Peter Wasserscheid, Jana Zaumseil Towards Ionic Liquid-based Thermoelectrochemical Cells Harvesting of Waste Heat Theodore J Abraham, Jennifer M Pringle, Douglas R MacFarlane for the VV5 Chair: Rika Hagiwara, Jenny Pringle Functional Ion Gels: Block Polymer/Ionic Liquid Composites for Advanced Applications Timothy Lodge, Dan Frisbie, Sipei Zhang, Keun-Hyung Lee, Yuanyan Gu Ionic Liquids Behave as Dissociable Liquids Matthew Allen Gebbie, Markus Valtiner, Banquy Xavier, Eric Fox, Wesley A Henderson, Jacob N Israelachvili Electrolytes for Energy Generation and Storage Applications Liyu Jin, Katherine Nairn, Patrick Howlett, Douglas MacFarlane, Maria Forsyth, Jenny Pringle Materialization of Ionic Liquids: Polymer Electrolytes of Ionic Liquids Masayoshi Watanabe Intermediate Phases of Ionic Solids and Liquids: Plastic- and Liquid Crystals of Fluorohydrogenate Salts Rika Hagiwara, Kazuhiko Matsumoto, Ryosuke Taniki, Fei Xu, Takeshi Enomoto Computational Study of Ionic Liquids Confined inside Amorphous Carbon Structures Joshua Monk, Ramesh Singh , Francisco R Hung ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 7 CONFERENCE REPORTS Modeling-based Study of the Effect of Diluents on Transport Properties of Ionic Liquid Electrolytes David Binion, Soumik Banerjee Surface Smoothing of Glass Substrate by Irradiation of Ionic Liquid Ion Beams Mitsuaki Takeuchi, Takuya Hamaguchi, Hiromichi Ryuto, Gikan H Takaoka VV6 Chairs: Masayoshi Watanabe, Rico E. Del Sesto Ionic Liquids as Low Cost and Versatile Organic Precursors for Carbonaceous Materials Shiguo Zhang, Kaoru Dokko, Masayoshi Watanabe Tough Block Copolymer Ion Gels via End-block Crosslinking Yuanyan Gu, Sipei Zhang, Luca Martinetti, Keun Hyung Lee, Lucas D. McIntosh, C. Daniel Frisbie, Timothy P. Lodge The Effect of Ionic Liquid Uptake and Self-assembled Conductive Network Composite Layers on Nafion(TM) Based Ionic Polymer Metal Composite Electromechanical Bending Actuators Dong Wang, Reza Montazami, James Randy Heflin Use of Ionic Liquids in Textile Finishing Klaus Opwis, Torsten Textor, Jochen Stefan Gutmann, Tom Welton, Agnieszka Brandt, S. M. Shahrul Nizan S. Z., Jason P. Hallett Self-templated Fluidic Precursor-based Carbons with Tailorable Pores and Their Application as Supercapacitor Electrodes Pasquale F. Fulvio, Patrick C. Hillesheim, Shannon M. Mahurin, Gabriel M. Veith, Sheng Dai High Temperature Solid-state Dye-sensitized Solar Cells Based on Organic Ionic Plastic Crystal Electrolytes Feng Yan A Novel PEO Based Poly (Ionic Liquid) Material for Energy Device Application Heyi Hu, Wen Yuan ___________________________________________________________________________ page 8 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS 5th International Congress On Ionic Liquids (COIL-5) April 21-25, 2013 • Vilamoura, Algarve, Portugal Modeling and Structure Pre-Symposium Opening - J. N. Canongia Lopes Cations With Polar Tails And The Role Of Anions In The X-Ray Scattering Of Ils C. J. Margulis, H. K. Kashyap, R. P. Daly, J.Hettige, H. V. R. Annapureddy Polarisability In Ionic Liquids C. Schröder, O. Steinhauser First Principles Approaches To Studying Ionic Liquids E. I. Izgorodina, J. Rigby, J. L. Hodgson, S. Tan Comparative Study Of The OKE Spectra And Physical Properties Of Branched And Linear Alkyl Chain Imidazolium Ionic Liquids L. Xue, F. Bardak, G. Tamas, E. Gurung, Y. P. Koh, S. L. Simon, E. L. Quitevis Heterogeneous Systems Containing Ionic Liquids: Interactions With Metal Surfaces And Carbon Nanomaterials A. S. Pensado, A. Podgorsek, A. C. F. Mendonça, J. M. P. França, A. A. H. Padua Dissecting The Interaction Energies In Protic Ionic Liquids K. Fumino, V. Fossog, K. Wittler, R. Hempelmann, R. Ludwig First Principle Prediction Of Ionic Liquid Melting Points E. Maginn, Y. Zhang Understanding The Competitive Influence Of Dispersive Interactions And H-Bonding In Structuring Imidazolium Based Ionic Liquids P. Hunt, R. P. Matthews Room Temperature Ionic Liquids With Fluorinated Tails: Evidences Of Triphilic Behaviour And Structural Implications A. Triolo, O. Russina, F. Lo Celso, S. Passerini, B. G. Appetecchi, A. Mele, R. Caminiti, F. Castiglione Iberian Meeting Pre-Symposium Opening - J. M. S. S. Esperança, I. M. Marrucho ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 9 CONFERENCE REPORTS Old Ammonium Salts To New Applications: Transformation Of Carbohydrates To 5-Hydroxymethylfurfural (HMF) S. P. Simeonov, J. A. S. Coelho, C. A. M. Afonso Ionic Liquids Or Ionic Sponges? Clean Enzymatic Process For Natural Flavour Ester Synthesis In Switchable Ionic Liquid/Solid Phases J. M. Bernal, A. Navarro, G. Sanchez-Gomez, G. Lopez-Lopez, P. Lozano Langmuir Films Of Ionic Liquids: Mono And Multilayering Of [Octadecylmim][Ntf2] And [Octadecylmim][Cl] At The Air-Water Interface C. Maia, P. Morgado, M. Rosamonte, M. Goldmann, J.-B. Sarrazin, J. N. Canongia Lopes, E. J. M. Filipe Can Ionic Liquid Dispersive Liquid-Liquid Microextraction Be Combined With Screen Printed Electrodes As Electrochemical Detectors? E. Fernández, L. Vidal, J. Iniesta, C. E. Banks, A. Canals FT-ICR Studies Of The Thermal Vaporization Of Aprotic And Protic Ionic Liquids M. E. Minas Da Piedade Towards Protic Ionic Liquid Electrolyte Membranes For Fuel Cells M. Díaz, A. Ortiz, M. Vilas, E. Tojo, I. Ortiz Rheology Of Ionic Liquids And Ionanofluids F. J. V. Santos, A. P. Ribeiro, J. França, F. Pimentel, S. Molias, C. A. Nieto De Castro Carvone Derived Ionic Liquids As Chiral Shift Reagents F. Santamarta, Y. Fall, E. Tojo Ionic Liquid Films As Water Vapor Sensors J. Restolho, J. L. Mata, R. Colaço, B. Saramago A Multiscale Research Strategy To Develop Gas Separation Process Based On Ionic Liquids J. Palomar Herrero, V. Ferro, N. Alonso, J. Bedia, J. Lemus, M. GonzálezMiquel, E. Ruiz, J. De Riva, C. Moya, M. A. Gilarranz, J. J. Rodriguez Task-Specific Ionic Liquids As Novel Smart Fluids Luis C. Branco, F. Pina Opening session Opening Remarks - L. P. N. Rebelo, J. N. Canongia Lopes ___________________________________________________________________________ page 10 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS The Balance Of Blue-Skies Research, Strategic Research, Innovation And Fashion For Economic Growth: Ionic Liquids As An Example (PL1) W. A. Wakeham Oral Session 1 Chair: L. Rebelo Pyrazolium-Based Ionic Liquids: Physico-Chemical And Structural Features Of Imi-Dazolium Isomers C. Chiappe, A. Sanzone, G. Raos, D. Mendola, F. Castiglione, A. Famulari, A. Mele Wound Dressings Through An Ionic Liquid Process – Filling A Gap In The Wound Care Sector G. Gurau, L. E. Block, J. Shamshina, R. D. Rogers Can Liquid-Crystalline Ionic Liquids Influence The Rate And/Or Selectivity Of Chemical Reactions? Y. Gao, J. M. Slattery, D. Bruce, J. N. Canongia Lopes, K. Shimizu Oral Session 2 Chair: H. Ohno Ion Pairs And Imidazolium-Based Ionic Liquids (PL2) B. Kirchner, M. Brehm, M. Brüssel, D. Fihara, O. Hollóczki, M. Kohagen, F. Malberg, A. S. Pensado, A. Stark, H. Weber Reaction Kinetics Of CO2 With Amine-Functionalized Ionic Liquids T. Gohndrone, B. Gurkan, M. Quiroz-Guzman, M. Aruni Desilva, J. F. Brennecke Surface Nanocrystallization Of Room-Temperature Ionic Liquids 09:30 Y. Jeon, D. Vaknin, W. Bu, J. Sung, Y. Ouchi, W. Sung, D. Kim Understanding The Charging Mechanism Of Supercapacitors From Molecular Simulations C. Merlet, B. Rotenberg, P. A. Madden, P-L. Taberna, P. Simon, Y. Gogotsi, M. Salanne Oral Session 3 Chair: P. Wassercheid Closing The Loop On Catalyst Design – XP As A Tool To Probe Catalyst Tuning In Ionic Liquids (PL3) M. Shuang, K. R. J. Lovelock, P. Licence ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 11 CONFERENCE REPORTS Polymeric Ionic Liquids: Broadening The Properties And Applications Of Polyelectrolytes D. Mecerreyes Green Ionic Liquids And Ionic Liquids In Liquid Colloidal Systems W. Kunz Protic Ionic Liquids - Interactions With Biomolecules Towards Functional Materials N. Byrne Oral Session 4 Chair: P. Licence Ionic Liquid Iconoclasts: New Developments In Ion Selection, Design And Synthesis For Protic, Mesothermal And Hydrated Ils (PL4) J. H. Davis Jr Surface-Active Ionic Liquids In Catalysis: Micellar Solutions Meet Microemulsions K. Bica, P. J. Gritsch, A. K. Ressmann, P. Gaertner, R. Zirbs, C. Schröder Following Reactions In Ionic Liquids Under Vacuum Conditions By In-Situ ARXP I. Niedermaier, C. Kolbeck, N. Taccardi, P. S. Schulz, P. Wasserscheid, H-P. Steinrück, F. Maier New Methodologies For Biomass Processing With Ionic Liquids W. Henderson Oral Session 5 Chair: M. Watanabe Nanostructure - Function Relationships In Ionic Liquids (PL5) R. Atkin Solvation Dynamics In Ionic Liquids M. Liang, X-X. Zhang, D. Roy, N. Ernsting, M. Maroncelli Liquid Crystalline Supported Ionic Liquid Phase (LC-SILP) Materials P. Wasserscheid Oral Sessions 6 & 7 Chair: J. Brennecke What Is Special For Charge Transport In Ionic Liquids? ___________________________________________________________________________ page 12 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS M. Watanabe Generation Of Silicon Nanoparticles With Plasma Electrochemistry N. Spitczok V. Brisinski, A. Lahiri, O. Höfft, F. Endres Synthesis Of New Brønsted Acid Ionic Liquids And Their Application In The Hydrolysis Of Biomass W. M. Reichert, M. La, N. G. Williams, T. Goode, A. Mirjafari, J. H. Davis, Jr. Fluoroorganic And Cyano-Based Ionic Liquid Anions - Assessment Of (Eco)Toxicity, Biodegradability And Hydrolytic Stability S. Stolte, S. Steudte, J. Neumann, J. Thoeming, P. Stepnowski Functional Surfaces From Ionic Liquids – From Batteries To Corrosion And Wear Performance M. Forsyth, D. R. Macfarlane, P. C. Howlett How Do Supported Ionic Liquids Behave Under Thermal Stress? F. Heym, C. Kern, W. Korth, A. Jess Metallocenium Ionic Liquids: Physical Reactivities T. Mochida, Y. Funasako, T. Inagaki Properties And Chemical Electrodeposition Of Copper And Nickel Composites From Deep Eutectic Solvents A. P. Abbott, K. El Ttaib, G. Frisch, K. S. Ryder Oral Session 8 Chair: D. MacFarlane Ionic Liquid Pretreatment: Are We There Yet? B. A. Simmons Nanotribology And Interfacial Studies Of Ionic Liquids M. W. Rutland Design And Application Of Ionic Liquids Changing Their Hydrated State By Temperature H. Ohno, Y. Kohno On The Catalytic Properties Of Transition-Metal Catalysts On Ionic Liquids J. Dupont Oral Session 9 Chair: Y. Mo-Koo ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 13 CONFERENCE REPORTS Tuning The Properties Of Ionic Liquids: Size-, Charge-And Volume-Effects I. Krossing From Diionic Ionic Liquids To Polymer-Like Materials C. Chiappe, C. S. Pomelli Electron-Donating Ionic Liquids: Connecting Reactivity And Structure M. Liang, M. F. Thomas, J. A. Devine, S. Khatun, E. W. Castner, Jr. Oral Session 10 A Chair: T. Welton Towards The Hydrogen Economy - Ionic Liquids For High Efficiency Water Oxidation D. R. Macfarlane Investigation Of Ionic Liquid Monomers And Polymerized Ionic Liquids With Spin Probes V. Strehmel, P. Strauch, S. Berdzinski, M-P. Ruby Functional Materials Based Upon Ionic Liquids: From Liquid-Crystals To Conducting Polyelectrolytes M. A. Firestone Nano-Structure And Stick-Slip Friction In Confined Pyrrolidinium-Based Ionic Liquid Films A. M. Smith, K. R. J. Lovelock, S. Perkin Formation Of Metallic Nanoparticles And Nanoalloys In Ionic Liquids: Synthetic Routes And Mechanisms I. Helgadottir, W. Darwich, P. H. Haumesser, C. C. Santini Oral session 10 B Chair: E. Maginn Separation Of Collective And Single-Particle Dynamics In PyridiniumBased Ils Using Polarized Neutrons J. P. Embs, T. Burankova, E. Reichert, V. Fossog, R. Hempelmann Closest Ion-Ion Interaction And Structural Heterogeneity Of 1Alkylimidazolium Based Protic Ionic Liquids Y. Umebayashi, H. Hamano, H. Doi, X. Song, R. Kanzaki, K. Fujii, Y. Kameda Experimental And Theoretical Study On Infinite Dilution Activity Coefficients Of Various Solutes In Piperidinium Ionic Liquids U. Domanska, K. PaduszyńSki ___________________________________________________________________________ page 14 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Electrochemical Windows Of Room-Temperature Ionic Liquids From Molecular Dynamics And First Principles Calculations S. Ping Ong, O. Andreussi, Y. Wu, N. Marzari, G. Ceder The General Phase Behaviour Of Mixtures Of 1-Alkyl-3Methylimidazonium Bis(Trifluoromethylsulfonyl)Amides With NAlkylalcohols B. Rathke, W. Schröer Oral session 10 C Chair: C. Castro Absorption Heat Pumps Working With Ionic Liquids D. S. Ayou, J. C. Bruno, A. Coronas Tribological Properties And Solubility Of Phosphonium Ionic Liquids As Lubricant Additives J. Dyck, T. Graham, I. Wiater-Protas, J. Clyburne Ionic Liquid Assisted Nano-Carrier For Drug Delivery Systems M. Goto Recent Progress In KOEI’s Ionic Liquids T. Sumida, M. Nishida On The Hunt: Ionic Liquids For Biomedical Coatings U. Kragl, F. Stein, S. Petersen, S. Kaule, K. Sternberg Oral session 11 A Chair: L. Santos Ionic Liquids As A Chemical Platform For Membrane Design And Applications R. D. Noble, D. L. Gin Dual-Controlled Fluorophore Release From Enhanced Viscoelastic Imidazolium- Based Ionogels S. Gallagher, A. Kavanagh, L. Florea, R. Byrne, D. R. Macfarlane, K. J. Fraser, D. Diamond In Situ Electron Microscope Observation Of Chemical Reactions In Ionic Liquids S. Kuwabata, T. Uematsu, T. Torimoto, T. Tsuda Sol-Gel In Ionic Liquids. Influence Of The Anions On The Morphology And Texture Of Ionogels L. Viau, M-A. Néouze, S. Volland, D. Brevet, A. Galarneau, A. Vioux ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 15 CONFERENCE REPORTS Luminescent Polymer Materials From Ionic Liquids P. Campbell, A-V. Mudring Oral session 11 B Chair: U. Domanska Effects Of Ionic Liquids On The Enzymatic Activity Of Proteins S. Weibels, C. Herrmann, H. Weingaertner CO2 Removal From Anaesthetic Gas Circuits By Enzymatic Bioconversion With Task Specific Ionic Liquids L. A. Neves, C. Martins, C. A. M. Afonso, I. M. Coelhoso, J. G. Crespo Ionic Liquid Process For Mercury Removal In Petrochemical Industries M. P. Atkins, J. D. Holbrey, Y. C. Kuah, P. Nockemann, G. Srinivasan, K. R. Seddon, Y. Zou Design Of Ionic Liquids For Direct Extraction Of Lignin From Wood Chips T. Itoh, Y. Hamada, K. Yoshida, R-I. Asai Efficient Fractionation Of Wood: Spinchem® Reactor And Switchable Ionic Liquids V. Eta, I. Anugwom, P. Virtanen, P. Mäki-Arvela, J-P. Mikkola Oral Session 11 C Chair: K. Massone Ionic Liquid And Polymeric Ionic Liquid-Based Microextraction Methods For The Analysis Of Pharmaceutical Impurities And Nucleic Acids J. L. Anderson, T. D. Ho, H. Yu, T. Li, W. T. S. Cole Ionic Liquids – A Superior Reaction Media For Organic Syntheses With Dangerous Reagents N. V. Ignat’ev, M. Schulte, S. G. Zlotin, N. N. Makhova, A. B. Sheremetev, Y. A. Serguchev, Y. G. Shermolovich Ionic Liquid-Functionalized Ordered Mesoporous Silicas For Selective Alcohol Oxidation M. T. Heinze, W-D. Einicke, A. Stark, R. Gläser Ionic Liquids As Media In Absorption Heat Transformer T. J. S. Schubert, S. Sauer, C. Römich, N. Merkel, M. Gleiß, L. Hösterey, K. Schaber Ionic Liquid-Liquid Separations: A New Approach M. J. Earle ___________________________________________________________________________ page 16 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Flash oral session A Chair: C. Pereira Ionic Liquids As Soluble Support In Organic Synthesis A. Kumar Syntheses Of The Transition Metal Complex-Functionalized Ionic Liquids And Their Application To Catalysis H. You, S. Chen, H. Wu, Y. Liu Multifunctional Ionic Liquids From Cationic Metal-Chelate Complexes Y. Funasako, T. Mochida Ionogels With Carbon Aerogel M. Koel Room-Temperature Synthesis Of The Bi5[Gacl4]3 Salt From Three Different Classes Of Ionic Liquids J. Åkerstedt, L. Kloo, M. Gorlov Coordination Of Indium With Phosphine Oxide Functionalised Ionic Liquids S. Olejarz, M. Swadzba-Kwasny, H. Q. Nimal Gunaratne, P. Nockemann Imidazolium-Based Ionic Liquids And Imidazoles: Comparing Properties, Performances And Possibilities J. E. Bara, C. Heath Turner, S. P. Verevkin, M. S. Shannon, W. J. Horne, M. S. Hindman, A. C. Irvin, A. Stanton, J. W. Whitley, H. Liu Spectroscopic Identification Of Reactants, Intermediates And Product In The Biomass Conversion In Ionic Liquids E. A. Khokhlova, V. V. Kachala, V. P. Ananikov Direct HPLC Analysis Of Cellulose Depolymerization By Ultrasonication In Ionic Liquids K. Kuroda, Y. Fukaya, H. Ohno Fractionation Of Hemi-Rich Pulp Into Cellulose And Hemicellulose Using An IL/ Cosolvent Mixture C. Froschauer, M. Hummel, M. Iakovlev, A. Roselli, G. Laus, H. Schottenberger, H. Sixta Ionic Liquids As Extracting Phases For Nanoparticles: Consequences On The Toxicity Of Aqueous Phases S. Viboud, N. Papaiconomou, C. Payrard, D. Fontvieille An Enzymatic Biofuel Cell Using Hydrophobic Ionic Liquids As Electrolytes M. Masuda, N. Nakamura, H. Ohno ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 17 CONFERENCE REPORTS Development Of Recyclable Ionic Liquids For Biomass Processing A. W. T. King, A. Parviainen, A. J. Holding, I. Mutikainen, I. Kilpeläinen New Insights In The Extraction Mechanism Of Suberin By Cholinium Hexanoate R. Ferreira, H. Garcia, A. Sousa, C. Freire, A. Silvestre, W. Kunz, L. P. N. Rebelo, C. Silva Pereira Extraction Of 5-Hydroxymethylfurfural Understanding Molecular Interactions A. Stark, D. H. Zaitsau, S. Verevkin From Ionic Liquids: CO2 Capture By Bio-Ionic Liquids P. Sanglard, E. Vanoli Flash oral session B Chair: A. Pádua Ion Speciation Of Protic Ionic Liquids In Water: Transfer From Contact To Solvent-Separated Ion Pairs P. Stange, K. Fumino, R. Ludwig How A Subsequent Methylation Of The Imidazolium Ring Affects The Thermochemical Properties Of Ils S. P. Verevkin, Dz. H. Zaitsau, A. V. Yermalayeu, V. N. Emel’yanenko, R. Ludwig, C. Schick, Y. Zhang, E. J. Maginn The Molecular Structure Of Mixtures Of Ionic Liquids I. J. Villar-Garcia, F. Cameron, J. P. Hallett, T. Welton Nanostructure Of Fluorous Protic Ionic Liquids Which Contain Hydrocarbon, Fluorocarbon And Polar Domains T. Greaves, D. Kennedy, Y. Shen, G. Song, C. Drummond Upper Limit Challenge For The Enthalpy Of Vaporization Of Ionic And Molecular Compounds With Quartz Crystal Microbalance D. H. Zaitsau, S. P. Verevkin Hydrogen Bonding In Protic Ionic Liquids R. Hayes, S. Imberti, G. G. Warr, R. Atkin Temperature Of Maximum Density (TMD) Of Ionic Liquid Aqueous Solutions M. Tariq, J. M. S. S. Esperança, M. R. C. Soromenho, L. P. N. Rebelo, J. N. Canongia Lopes Physicochemical And Structural Properties Of Ionic Nanofluids Y. U. Paulechka, M. P. Shevelyova, G. J. Kabo, A. V. Blokhin, A. G. Kabo, T. ___________________________________________________________________________ page 18 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS N. Levitskaya Ionic Association And Interactions In Ionic Liquid + Water Systems B. E. Mbondo Tsamba, J. M. Andanson, M. F. Costa Gomes, S. Sarraute, M. Traikia, P. Husson Accurate Volatility Study Of 1-Ethyl-2-Alkylpyridinium Bis(Trifluoromethylsulfonyl) Imide Ionic Liquid Series M. A. A. Rocha, A. S. M. C. Rodrigues, M. Vilas, E. Tojo, E. Sapei, L. M. N. B. F. Santos Investigation Of Imidazolium Based Aprotic Heterocyclic Anion (AHA) Ionic Liquids Using NMR M. A. Desilva, S. Seo, C. Shi, M. Massel, J. F. Brennecke Study Of Thermochromic Effect In Newly Synthesized 1-(2-Hydroxyethyl)3- Methylimidazolium Nitrate Ionic Liquid S. Dozic, M. Vranes, S. Gadzuric Probing Structure And Nano-Segregation In Rtils - 129Xe NMR And MD Simulations P. Morgado, K. Shimizu, J. M. S. S. Esperança, E. J. M. Filipe, J. N. Canongia Lopes Computer-Aided Molecular Design Of Ionic Liquids: Prediction Of Melting Point D. C. Weis, D. R. Macfarlane Simulation Studies Of Dynamic Properties In An Organic Ionic Plastic Crystal [P1224]+[PF6]F. Chen, L. Jin, S. W. Deleeuw, P. Howlett, J. M. Pringle, M. Forsyth Flash Oral Session C Chair: R. Rogers Photo-Reposnsive Hydrogels Based On Phosphonium Poly-Ionic Liquid B. Ziółkowski, D. Diamond Fluorescent Calcium Carbonate Microcapsules: From Ionic Liquid Structuring At Interfaces To Functional Materials M. Kowacz, J. M. S. S. Esperança, L. P. N. Rebelo Ultraslow Dynamics At Crystallization Of Methylimidazolium-Based Ionic Liquids K. Nishikawa, H. Seki, M. Imanari Controlling The Properties Of Energetic Ionic Liquids Through, The Incorporation Of Reactive Nanomaterials P. D. Mccrary, S. A. Alaniz, R. D. Rogers ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 19 CONFERENCE REPORTS Formation Of Au Particles In Nanoconfined Ionic Liquids By Low Energy Quantum Beam Irradiation A. Imanishi, T. Arimura, T. Sakamoto, T. Tsuda, S. Kuwabata, K-I. Fukui Introduction Of Third Generation Solvent System: Electro-Reduction Of Organic Molecules O. Abdul-Rahim, T. Ruether, P. Permutter, A. M. Bond Liquid Metal Salts: Ionic Liquids For High Current Density Electroplating Of Copper And Silver S. Schaltin, N. R. Brooks, J. Sniekers, K. Binnemans, J. Fransaer Dysprosium-Based Polymeric Ionic Liquid: A Renewable Catalyst For Multicomponent Reactions At 353 K And A Single Chain Magnet At Low Temperatures D. Prodius, F. Macaev, Y. Lan, N. Sucman, G. Buth, V. Mereacre, C. E. Anson, A. K. Powell A Comparative Study Of The Solid-Fluid Transitions Of Hmim (Pfbu)SO3 And NB4 (Pfbu)SO3: New Fluorinated Domain A. B. Pereiro, M. J. Pastoriza-Gallego, K. Shimizu, I. M. Marrucho, J. N. Canongia Lopes, M. M. Piñeiro, L. P. N. Rebelo Dyeing Of Textile Materials In Ionic Liquids K. Opwis, D. Knittel, J. S. Gutmann Using An Ionic Liquid Platform For The Development Of Materials For The Extraction Of Uranium From Seawater P. S. Barber, C. S. Griggs, S. P. Kelley, S. Wallace, R. D. Rogers Ionic Liquids As A Nice Environment For Metal Ions C. Silvio Pomelli, C. Chiappe, T. Ghilardi, A. Barsanti Ionic Liquids Containing Transition Metal Functional Groups For CO2 Capture J. Huang, H. Liu, I. H. J. Arellano, A. E. Rosamilia, A. Warden, P. Pendleton Metal Recycling In Deep Eutectic Solvents G. Frisch, A. P. Abbott, J. Hartley Phosphonium Ionic Liquids As Carriers Of Metal Ions From Chloride Solutions In Separation Processes M. Regel-Rosocka, M. Baczynska, M. Wisniewski Removal And Recovery Of Ionic Liquids From Contaminated Water Streams Using Aluminium-Based Salts C. M. S. S. Neves, M. G. Freire, J. A. P. Coutinho ___________________________________________________________________________ page 20 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Oral session 12 Chair: A. Mudring Mixtures Of Ionic Liquids T. Welton What Chance For Inorganic Ionic Liquids? C. Austen Angell, I. Klein, T. G. Tucker, Z. Zhao New And Optimized NMR Methods For Probing Distances And Interactions In Ionic Liquids R. Giernoth Electrochemical Deposition And Capacitance Of Composites Of Carbon Nanotubes And Conducting Polymers In Ionic Liquids X. Zhou, G. Z. Chen Oral session 13 Chair: J. Lopes Electron Transfer Reactions In Ionic Liquids J. F. Wishart, M. Gohdo, R. Rached, M. Harries, R. Crowell, H. Y. Lee, E. W. Castner, Jr., M. Liang Absorption And Transport Of Molecular Solutes In Ionic Liquids S. Stevanovic, D. Almantariotis, M. C. Gomes Application Of Brønsted Acid Ionic Liquids/Zwitterions In Pd-Catalyzed Ethylene Methoxycarbonylation - Effect On Stability And Catalytic Activity E. J. García Suárez, A. Riisager, R. Fehrmann, S. G. Khokarale The Use Of Ionic Liquids And Ionic Polymers To Mediate Enantioselective Diels-Alder Reactions P. Goodrich, L. Hall, M. Muldoon, S. Doherty, J. Ellison, V. Parvulescu, C. Hardacre Poster Session 1 Ionic Liquids As Soluble Support In Organic Synthesis A. Kumar Ionothermal Synthesis: Tuning The Framework Type With Ionic Liquids A. Stark, M. Mohsin Azim, R. Gläser Ionic Liquids Synthesis: Kinetic Measurements And Chemical Reactor Modeling ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 21 CONFERENCE REPORTS D. S. Firaha, Y. U. Paulechka, V. N. Pavlechko Syntheses Of The Transition Metal Complex-Functionalized Ionic Liquids And Their Application To Catalysis H. You, S. Chen, H. Wu, Y. Liu Dicationic Ionic Liquids In Condensation Reactions Of Some Organic Compounds E. Priede, L. Anteina, A. Gaidule, A. Zicmanis Belousov-Zhabotinsky Reaction In Protic Ionic Liquids T. Ueki, M. Watanabe, R. Yoshida Protodecarboxylation Reactions And Decarboxylative Cross Coupling Reactions With Recyclable Nanoscale Catalyst In Ionic Liquids M. T. Keßler, C. Gedig, S. Robke, M. H. G. Prechtl Design Of Bi-Functionalized Ionic Liquids For Catalysis V. M. Manzanares, Z. Fei, P. J. Dyson Selective Gas Phase Hydrogenation Of 1,3-Butadiene Using A Solid Catalyst With Ionic Liquid Layer (SCILL) T. Mangartz, W. Korth, A. Jess Alkylsulfates Ils Stability With Water/Alcohols: A Thermodynamic Approach Towards The Synthesis Of New Ils J. Jacquemin, P. Goodrich, W. Jiang, D. Rooney, C. Hardacre Catalytic “Triangles”: Binding Of Iron In Task-Specific Ionic Liquids D. Prodius, F. Macaev, E. Stingaci, V. Pogrebnoi, V. Mereacre, G. Novitchi, G. E. Kostakis, C. E. Anson, A. K. Powell Synthesis, Characterization And Application Of New N-, O- And SFunctionalized Task Specific Ionic Liquids I. M. Mertens, N. Taccardi, P. S. Schulz, P. Wasserscheid Low-Viscous Ionic Liquids With Cyanoborate Anions M. Finze, J. A. P. Sprenger, W. Frank, N. V. Ignatiev, M. Schulte Ionic Liquids With Aprotic Heterocyclic Anions And Their Reactivity With Water And CO2 M. Quiroz-Guzman, M. A. Desilva, J. F. Brennecke Molten Salt Modified SCILL-Catalysts For Methanol Steam Reforming M. Kusche, S. Bajus, H. Niedermeyer, F. Agel, A. Bösmann, P. Wasserscheid New Metal-Containing Ionic Liquids With Phosphine And Phosphinite Functionality A. G. Zazybin, V. K. Yu, K. D. Praliyev, A.Y. Ten, N. U. Kystaubayeva, D. Y. ___________________________________________________________________________ page 22 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Nurmukhambetov, S. I. Ospanova, B. M. Khudaibergenov, A. A. Abdulina, N. A. Yelubayeva, M. G. Batyrov, N. Khairlybaeva, S. A. Yerkimbekova Multifunctional Ionic Liquids From Cationic Metal-Chelate Complexes Y. Funasako, T. Mochida Ionogels With Carbon Aerogel M. Koel Preparation Of Fluorophilic Ionic Liquids As Solvents For Fluorinated Polymers A. Tsurumaki, H. Ohno Ionic Liquids With Highly Acidic Protons - Application As Catalysts And Solvents In Biphasic Reaction P. S. Schulz, K. Tietze-Frech, P. Wasserscheid, N. Ignatiev Synthesis And Properties Of Oliqoalkylnaphtenic Synthetic Oils In The Presence Of Ionic-Liquid Catalysts A. H. Azizov, R. V. Aliyeva, Kh. H. Seidova Inducing The Formation Of High-Order Polybromide Monoanions With Ionic Liquids M. E. Easton, A. J. Ward, A. F. Masters, T. Maschmeyer Isomerisation Of Α-Pinene Oxide Over Supported Ionic Liquid Catalysts (Silcas) For Production Of Campholenic Aldehyde E. Salminen, P. Virtanen, N. Kumar, P. Mäki-Arvela, J-P. Mikkola Synthesis Of New 1-Ethyl-2-Alkylpyridinium (Trifluoromethanesulfonyl)Imide Ionic Liquids M. Vilas, M. A. A. Rochas, L. M. N. B. F. Santos, E. Tojo Bis Equilibrium Potentials Of Sn-Na Alloys As A Negative Electrode For Sodium Secondary Battery Using Nafsa-KFSA Intermediate Temperature Ionic Liquid T. Yamamoto, T. Nohira, R. Hagiwara, A. Fukunaga, S. Sakai, K. Nitta, S. Inazawa Use Of Ionic Liquids For Finishing PET Fabrics With Cellulose To Prepare “Cotton-Like” Surfaces T. Textor, J. S. Gutmann Ionic Liquids For The Nanosilicon Synthesis L. A. Aslanov, V. N. Zakharov, A. V. Yatsenko Cyclic Voltammetry And In-Situ Spectroelectrochemistry For The Electrodeposition Of Si(1-X)Gex From An Ionic Liquid A. Lahiri, O. Höfft, S. Z. El Abedin, F. Endres ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 23 CONFERENCE REPORTS Ionic Liquids For Energy Storage Applications, Imidazolium Or Pyrrolidinium? L. Chancelier, C. Santini, T. Gutel, S. Mailley, A. O. Diallo, C. Len, G. Marlair Influence Of The Composition Of Carboxilated-Based Protic Ionic Liquids On The Electrodeposition Process Of Nanocrystalline Ni° R. Ortega-Borges, S. López-León, E. Cuara-Diaz, G. Brisard, G. Trejo-Córdova, Y. Meas-Vong Protic Ionic Liquids For Electrochemical Hydrogen Peroxide Production C. Mcdonnell-Worth, A. Izgorodin, D. R. Macfarlane In Situ IV-SFG Studies On Interfacial Structures Of Ionic Liquids And Their Li-Salt Mixtures On Metal Electrodes W. Zhou, Y. Sakai, T. Iwahashi, D. Kim, Y. Ouchi Effect Of Lithium Salt Species On Electrochemical Properties Of Liquid Zwitterion M. Suematsu, M. Yoshizawa-Fujita, Y. Takeoka, M. Rikukawa Electrochemical Behaviour Of Ferrocene In Various Pure Ionic Liquids T. H. Ho, C. Gabrielli, H. Perrot, M. Turmine Loading-Controlled Stiffening And Pressure Effects In Ionic Liquids Confined In Nanoporous Silica G. Ori, F. Villemot, L. Viau, A. Vioux, B. Coasne Thermo-Reversible Ion-Gel Based On LCST-Type Self-Assembly Of Triblock Copolymers In An Ionic Liquid Y. Kitazawa, T. Ueki, S. Imaizumi, T. P. Lodge, M. Watanabe Photo-Reposnsive Hydrogels Based On Phosphonium Poly-Ionic Liquid B. Ziółkowski, D. Diamond On The Electrochemical Phase Formation In Air And Water Stable Ionic Liquids A. Ispas, I. Efimov, F. Endres, T. Carstens, A. Bund Towards Protic Ionic Liquid Electrolyte Membranes For Fuel Cells M. Díaz, A. Ortiz, M. Vilas, E. Tojo, I. Ortiz Preparation Of 3D Micro/Nano-Structures By Irradiation Of Quantum Beam Into Room-Temperature Ionic Liquid H. Minamimoto, T. Tsuda, A. Imanishi, S. Seki, S. Kuwabata Fluorescent Calcium Carbonate Microcapsules: From Ionic Liquid Structuring At Interfaces To Functional Materials M. Kowacz, J. M. S. S. Esperança, L. P. N. Rebelo ___________________________________________________________________________ page 24 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Lithium Solvate Ionic Liquid For Post Lithium-Ion Batteries K. Ueno, R. Tatara, H. Kwon, A. Yamazaki, T. Mandai, N. Tachikawa, K. Dokko, M. Watanabe Ionic Liquids: Opportunities For Hydrogen Storage M. H. G. Prechtl Dihydroxyl Imidazolium Ionic Liquids: Solvent, Ligand And Reducing Agnet In Metallic Nanoparticles Synthesis W. Darwich, C. Gedig, M. H. G. Prechtl, C. Santini Redox-Active Ionic Liquids In Energy Storage: Application To Li-Ion Batteries For Protection Against Overcharging D. Rochefort, B. Gélinas, J. Forgie, S. El Khakani, D. Macneil Electrochemical Properties Of Palladium Electrode In Protic Ionic Liquids N. Tachikawa, J. M. Pringle, D. R. Macfarlane Intermediate Temperature Lithium Secondary Batteries Using Alkali Amide Ionic Liquids T. Nohira, J-J. Lee, T. Matsui, T. Koketsu, K. Numata, T. Fujimori, K. Matsumoto, R. Hagiwara, K. Ui Formation Of Au Particles In Nanoconfined Ionic Liquids By Low Energy Quantum Beam Irradiation A. Imanishi, T. Arimura, T. Sakamoto, T. Tsuda, S. Kuwabata, K-I Fukui Novel Lyotropic Liquid-Crystalline Systems Containing Aprotic Amino Acid Ionic Liquids As Solvents K. Fujimura, T. Ichikawa, M. Yoshio, T. Kato, H. Ohno Electrodeposition Of Lithium/Polymer Composite Electrodes From An Ionic Liquid A. Willert, A. Prowald, S. Z. El Abedin, N. Borisenko, F. Endres Structures And Dynamics Of Ionic Liquid/Metal Electrode Interfaces J. Plöger, J. Anton, T. Jacob Functionalization Of Oxide Surfaces Through Reaction With 1,3Dialkylimidazolium: A Synchrotron-Radiation Photoelectron Study M. Laurin, Y. Lykhach, S. Schernich, N. Taccardi, N. Tsud, T. Skála, K. C. Prince, H-P. Steinrück, V. Matolín, P. Wasserscheid, J. Libuda A New Biosensor Based On A Combination Of Imidazolium Groups And Gold Nanoparticles With Mesoporous Silica L. Pereira Da Costa, C. M. Maroneze, A. Rahim, N. Fattori, F. A. Sigoli, I. O. Mazali, Y. Gushikem Ionic Liquids In Solid State: Glasses Or Crystals? ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 25 CONFERENCE REPORTS O. Cabeza, J. Vila, E. Rilo, S. Yáñez-Villar, M. A. Señarís-Rodríguez, L. M. Varela Synthesis And Physical Properties Of New Layered Silicates Based On Ionic Liquids: Application To A Biopolymer Matrix L. Sebastien, V. Bugatti, E. P. Giannelis, J. Duchet-Rumeau Application Of Ionic Liquids In Mg-Air Battery Y. Yan, M. Forsyth, P. Howlett Novel Polymer Electrolyte Based On Gellan And Ionic Liquids M. J. Neto, M. Fernandes, J. M. S. S. Esperança, M. J. Medeiros, V. De Zea Bermudez, M. M. Silva Task-Specific Ionic Liquids As Novel Smart Fluids L. C. Branco, F. Pina Electrochromic Ionic Liquid Based On Viologens N. Jordão, L. Cabrita, F. Pina, L. C. Branco Ionic Liquid Films As Water Vapor Sensors J. Restolho, J. L. Mata, R. Colaço, B. Saramago Continous Anion Exchange Of Ionic Liquids P. Keil, A. König, M. Kick Ionic Liquids As Adjuvants In Polyethylene Glycol + Potassium Phosphate Salts-Based Aqueous Two-Phase System R. L. De Souza, V. C. Campo, S. P. M. Ventura, J. A. P. Coutinho, C. M. F. Soares, A. S. Lima Dyeing Of Textile Materials In Ionic Liquids K. Opwis, D. Knittel, J. S. Gutmann Magnetic Stimuli-Responsive Supported Ionic Liquid Membranes For CO2 Transport E. Santos, J. Albo, C. Daniel, C. Portugal, J. Crespo, A. Irabien Combining Ionic Liquids And Polyethylene Glycols To Boost The Hydrophobic- Hydrophilic Range Of Aqueous Biphasic Systems J. F. B. Pereira, L. P. N. Rebelo, R. D. Rogers, J. A. P. Coutinho, M. G. Freire On The True Fire Hazard Investigation Of Ionic Liquids A. O. Diallo, C. Len, G. Marlair Understanding And Controlling Fractional Free Volume In Ionic LiquidBased Polymer Membranes For CO2 Capture M. S. Shannon, A. C. Irvin, M. S. Hindman, W. J. Horne, J. E. Bara ___________________________________________________________________________ page 26 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Removal Of Ionic Liquids From Aqueous Solutions By Adsorption Methods C. M. S. S. Neves, J. Lemus, M. G. Freire, J. Palomar, J. A. P. Coutinho Desulfurization Of Fuels Through Selective Extraction Using Ionic Liquids In Membrane Contactors A. R. Ferreira, L. A. Neves, J. C. Ribeiro, F. M. Lopes, I. M. Coelhoso, J. A. P. Coutinho, J. G. Crespo Ionic Liquids As New Absorbants For The Removal Of Hydrophobic Volatile Compounds J-P. Bazureau, G. Quijano, A. Couvert, A. Amrane, G. Darracq, L. Paquin, D. Carrie Imidazolium IL-Based Di- And Tri-Block Copolymers And The Effect Of Nanostructure On CO2/Light Gas Separations E. F. Wiesenauer, P. T. Nguyen, B. S. Newell, T. S. Bailey, R. D. Noble, D. L. Gin Pre-Concentration Of Bisphenol A From Human Body Fluids Using IonicLiquid-Based Aqueous Biphasic Systems H. Passos, A. C. A. Sousa, M. R. Pastorinho, A. J. A. Nogueira, L. P. N. Rebelo, J. A. P. Coutinho, M. G. Freire Introduction Of [Hemim][Ntf2] & [Bzmim][Ntf2] New Functionalized Ils To Improve Extraction Of Aromatic Compounds From A Petroleum Fraction A. N. Ahmadi, A. A. Safekordi, F. Fateminasab, A. Mehdizadeh, A. H. Jalili Application Of Alkyl Sulfate And Nitrate Imidazolium Based Ionic Liquids In Deep Desulfurization Of Model Diesel Fuels A. Mehdizadeh, A. N. Ahmadi, F. Fateminassab, A. H. Jalili Extractive And Oxidative-Extractive Desulfurization Of Fuels With Ionic Liquids B. Rodríguez-Cabo, A. Soto, A. Arce 1-Alkyl-3-Methylimidazolium Acetate Ionic Liquids For Citrus Essential Oil Deterpenation S. Lago, H. Rodríguez, A. Soto, A. Arce The Effect Of The Anion On The Thermodynamics And Kinetics Of CO2 Absorption In Ionic Liquids M. Gonzalez-Miquel, J. Palomar, F. Rodriguez Ionic Liquids And Ionic Liquid-Mediated Dispersions Of Nanomaterials As High Performance Additives For Lubricants T. J. S. Schubert, M. Ahrens, H. Sahin Novel Electrolytes For Supercapacitors ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 27 CONFERENCE REPORTS T. J. S. Schubert, B. Blumenröder Aluminum Current Collector Corrosion In PYR14TFSI, PYR14FSI And PYR14FTFSI R-S. Kühnel, J. Reiter, S. Passerini, M. Winter, A. Balducci Using An Ionic Liquid Platform For The Development Of Materials For The Extraction Of Uranium From Seawater P. S. Barber, C. S. Griggs, S. P. Kelley, S. Wallace, R. D. Rogers Suitably Designed Zwitterions Stabilize Nano-Phase Separation Of Hydrophobic Ionic Liquids And Hydrophilic Ionic Liquids S. Taguchi, T. Ichikawa, T. Kato, H. Ohno Possibility Of Extraction Of Thiophene Using [BMPYR]-Based Ionic Liquids E. Lukoshko, U. DomańSka-Z Elazna Use Of Ionic Liquids Having High Water Content For The Solubilization Of Hydrophilic Reagents And Extraction Of Metal Ions From Aqueous Solutuions I. V. Pletnev, S. V. Smirnova, T. O. Samarina Formation Of Pure Liquid Salt Forms From Active Pharmaceutical Ingredients To Establish New Drug Delivery Systems With Superior Properties J. Shamshina, P. D. Mccrary, O. A. Cojocaru, G. Gurau, R. D. Rogers Ionic Liquids As A Nice Environment For Metal Ions C. S. Pomelli, C. Chiappe, T. Ghilardi, A. Barsanti New Strategies For The Design Of Poly(IL) CO2-Selective Membranes W. J. Horne, M. S. Shannon, J. E. Bara, K. Terrill, A. C. Irvin, A. D. Stanton, M. S. Hindman The Incorporation Of Facilitated Transport Agents Into Room Temperature Ionic Liquid Based Composite Membranes For CO2 Capture M. G. Cowan, W. M. Mcdanel, D. L. Gin, R. D. Noble Spectroscopic Identification Of Reactants, Intermediates And Product In The Biomass Conversion In Ionic Liquids E. A. Khokhlova, V. V. Kachala, V. P. Ananikov Direct HPLC Analysis Of Cellulose Depolymerization By Ultrasonication In Ionic Liquids K. Kuroda, Y. Fukaya, H. Ohno Highly Nanostructured Polyisobutylene-Based Polymeric Ionic Liquids As Novel Self-Healing Materials ___________________________________________________________________________ page 28 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A. Stojanovic, P. Zare, C. Appiah, F. Herbst, W. H. Binder Application Of Ionic Liquids Based Microwave Assisted Extraction Of Lichen Compounds L. Paquin, S. Komaty, S. Tomasi, D. Carrié, J-P. Bazureau Tetra-N-Butylphosphonium Hydroxide Enables Extraction Of Cellulose From Wet Biomass Under Mild Condition M. Abe, Y. Fukaya, H. Ohno Novel Scanning Electron Microscope Observation Method For Biological Specimens Using Ionic Liquid T. Tsuda, E. Mochizuki, S. Kishida, Y. Ishigaki, N. Nemoto, S. Kuwabata Synthesis Of Ionic Liquids With Boronic Acid And Their Cellulose Solubility E. Kishi, M. Yoshizawa-Fujita, Y. Takeoka, M. Rikukawa Fractionation Of Hemi-Rich Pulp Into Cellulose And Hemicellulose Using An IL/Cosolvent Mixture C. Froschauer, M. Hummel, M. Iakovlev, A. Roselli, G. Laus, H. Schottenberger, H. Sixta Stability Studies Of Proteins In Ionic Liquids R. Desai, M. Eppink, M. Streefland, R. Wijffels Red Dye Isolation From Fermentation Broth Using Ionic Liquid-Based Aqueous Biphasic Systems S. P. M. Ventura, V. C. Santos-Ebinuma, J. F. B. Pereira, M. F. S. Teixeira, A. Pessoa Jr., J. A. P. Coutinho Solubilities, Partition Coefficients And Surfactant Properties Of Ionic Liquids Based On Active Pharmaceutical Ingredients C. Florindo, J. M. M. Araújo, C. Matos, L. Branco, A. Costa, Z. Petrovski, L. P. N. Rebelo, I. M. Marrucho Amino Acid Ionic Liquid As An Efficient Cosolvent Of Dimethyl Sulfoxide To Realize Cellulose Dissolution At Room Temperature T. Itoh, K. Yoshida, R-I. Asai Applicability Of Various Ionic Liquids In Dry-Jet Wet Spinning Of Cellulose Solutions M. Hummel, A. Michud, L. K.J. Hauru, H. Sixta Ftir And Xrd Analysis Of Cellulose Regenerated From Eucalyptus Wood Solutions In Amimcl A. Casas, M. V. Alonso, M. Oliet, J. C. Dominguez, F. Rodriguez, P. Navarro Improvement Of Immobilization Process For Covalent Binding And ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 29 CONFERENCE REPORTS Adsorption Of Lipase Onto Hydrophobic Matrices Using Ionic Liquid N. B. Carvalho, B. T. Vidal, M. M. Pereira, S. Mattedi, M. A. I. Duro, J. A. P. Coutinho, V. L. Sierpe-Jeraldo, C. M. F. Soares, A. S. Lima Drug Specific, Tuning Of An Ionic Liquid’s Hydrophilic-Lipophilic Balance To Improve Water Solubility Of Poorly Soluble Pharmaceutical Ingredients P. D. Mccrary, P. A. Beasley, G. Gurau, P. S. Barber, R. D. Rogers Youth Involvement At The 18th Conference Of Parties And The Need For Climate Science Literacy P. D. Mccrary, G. P. Foy, K. E. Peterman, R. D. Rogers The Structure Of Ionic Liquids And Its Impact On Their Ecotoxicological Behaviour T. E. Sintra, S. P. M. Ventura, A. M. M. Gonçalves, J. L. Pereira, F. Gonçalves, J. A. P. Coutinho Separation Of Target Products Accumulated In Microalgae With Ionic Liquids D. Kobayashi, K. Fujita, N. Nakamura, H. Ohno Bio-Derived Ionic Liquids For Pretreatment Of Lignocellulosic Biomass K. Ninomiya, C. Ogino, K. Takahashi, N. Shimizu Bionic Liquids – Ionic Liquid Antibiotics R. Giernoth Preliminary Observations On The Histologycal Effect [EM2N(CH2)2OH][ESO4] In Zebrafish Epithelia S. Barja-Fernández, E. De Miguel, R. Alvarez-Otero, M. Vilas, E. Tojo Of Study Of Reutilization Of Ionic Liquid On Lignin Purification R. Prado García, X. Erdocia Iriarte, J. Labidi Separation Of Extracellular Polysaccharides Using Ionic-Liquid-Based Aqueous Biphasic Systems S. F. Carvalho, R. T. Neto, L. P. N. Rebelo, J. A. P. Coutinho, M. G. Freire The Influence Of Choline-Based Ionic Liquids On The Catalytic Behaviour Of Laccase From Trametes Versicolor M. M. Pereira, A. S. Lima, S. P. M. Ventura, J. A. P. Coutinho No-D NMR Analysis Of Cellulose In Ionic Liquids H. Kunimura, K. Kuroda, Y. Fukaya, H. Ohno Phase-Separable Ionic Liquids For Lignocellulose Processing A. J Holding, A. W. T. King, I. Kilpeläinen Ionic Liquids Or Ionic Sponges? Clean Enzymatic Process For Natural Flavour Ester Synthesis In Switchable Ionic Liquid/Solid Phases ___________________________________________________________________________ page 30 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS J. M. Bernal, A. Navarro, G. Sanchez-Gomez, G. Lopez-Lopez, P. Lozano Differences In Physical Properties Between Two Organic SuperbasesDerived, (DBN, DBU) Alkanol Amine Switchable Ionic Liquids I. Anugwom, J-P. Mikkola, P. Virtanen, P. Mäki-Arvela, V. Eta Development Of Recyclable Ionic Liquids For Biomass Processing A. W. T. King, A. Parviainen, A. J. Holding, I. Mutikainen, I. Kilpeläinen Processing Of Dissolving Pulp Cellulose In Ionic Liquids B. Sithole, N. Deenadayalu, Z. Tywabi Ionic Liquid Mediated Pretreatment Of Lignocellulose S. Hyvärinen, M. Vaher, D. Yu. Murzin, M. E. Lienque, M. Kaljurand, M. Koel, J-P. Mikkola Biopolymers Extraction From Bio-Wastes With Ionic Liquids M. Guerreiro, H. Garcia, R. Ferreira, C. Silva Pereira Evaluation Of Stability Of Lipase From Yarrowia Lipolytica In The Presence Of Ionic Liquids L. De Carvalho Iff, D. Do Carmo Simões, B. Dias Ribeiro, M. A. Zarur Coelho Influence Of Deep Eutectic Solvents On Proteasic Activity G. Neves Ricarte, B. Dias Ribeiro, M. A. Zarur Coelho Cholinium-Based Ionic Liquids With Pharmaceutically Active Anions J. M. M. Araújo, C. Florindo, A. B. Pereiro, L. P. N. Rebelo, I. M. Marrucho CO2 Solubility In 1-Ethyl-3-Methylimidazolium Bis(Trifluoromethyl¬Sulfonyl)Imide At High Pressures And Various Temperatures R. Hamidova, N. Schmotz, J. Safarov, I. Kul, A. Shahverdiyev, E. Hassel Liquid-Liquid Phase Equilibria Of Binary Tetrafluoroborate Ionic Liquids With Diols P. Papis, A. Makowska, J. Szydłowski Mixtures Containing High Pressure Phase Behaviour Of CO2, CH4, N2O And N2 In 1-Buthyl-3Methylimidazolium Dicyanamide: Experimental Measurements And SoftSAFT Eos Modeling L. M. C. Pereira, M. B. Oliveira, K. A. Kurnia, A. M. A. Dias, F. Llovell, L. F. Vega, P. J. Carvalho, J. A. P Coutinho. High Pressure Solubility Of CH4, N2, CO2, N2O In 1-Ethyl-3Methylimidazolium Methyl-Phosphonate: Experimental Measurements And Soft-SAFT Eos Modeling L. M. C. Pereira, M. B. Oliveira, A. M. A. Dias, F. Llovell, L. F. Vega, P. J. Carvalho, J. A. P Coutinho. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 31 CONFERENCE REPORTS Surface Tension Of Binary Mixtures Of Ionic Liquids With The Common Bistriflamide Anion: Experimental Measurements And Modeling With The Soft-SAFT Eos M. B. Oliveira, M. Domínguez-Pérez, M.G. Freire, F. Llovell, O. Cabeza, J. A. Lopes Da Silva, L. F. Vega, J. A. P. Coutinho Deep Eutectic Mixtures Of Ethanolamines With Fatty Acids G. J. Maximo, M. C. Costa, J. A. P. Coutinho, A. J. A. Meirelles Solid-Liquid Equilibrium Of Choline Chloride With Polycarboxylic Acids: Characterization Of The Phase Diagram And Properties Of The Mixtures G. J. Maximo, M. C. Costa, J. A. P. Coutinho, A. J. A. Meirelles LCST-Type Phase Transition Of Ionic Liquid/Water Mixture Enables Comparison Of Hydrophilicity Of Added Ions S. Saita, Y. Kohno, H. Ohno The Impact Of Water And Metal Ions On The Transport Properties And Structure Of A Long Chain Imidazolium Chloride Ionic Liquid N. Goujon, N. Byrne, T. Walsh, M. Forsyth G-Quadruplex Formation In Hydrated Ionic Liquids K. Fujita, H. Ohno Solubilities Of CO2 In Aqueous Solutions Of Monoethanolamine And Dicyanamide-Based Ionic Liquid H. Gao, F. Xu, H. Dong, X. Zhang, S. Zhang The Influence Of Diols Structure On Miscibility With Ils E. Sztank, A. Makowska, J. Szydłowski Excess Molar Volumes For The Ternary Systems (IL + An Alkanol + Nitromethane) At T= (303.15 Or 313.15) K N. Deenadayalu, I. Bahadur Polymorphism And Thermal Behaviour Of Bis(Fluorosulfonyl)Amide Salts K. Matsumoto, T. Oka, T. Nohira, R. Hagiwara Binary Mixtures Of Ionic Liquids In Aqueous Solution: Toward An Understanding Of Their Salting-In/Salting-Out Phenomena M. G. Freire, C. M. S. S. Neves, B. Schröder, K. Shimizu, L. M. N. B. F. Santos, J. A. P. Coutinho, I. M. Marrucho, L. P. N. Rebelo, J. N. Canongia Lopes Ion Speciation Of Protic Ionic Liquids In Water: Transfer From Contact To Solvent-Separated Ion Pairs P. Stange, K. Fumino, R. Ludwig The Ion Pair Formation Of Imidazolium Based Ionic Liquids In Highly ___________________________________________________________________________ page 32 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Diluted Solutions E. Schmidt, R. Ludwig On The Molecular Mechanism Of The Solubility Of Gases In Ionic Liquids D. Kerlé, D. Paschek, R. Ludwig Solute Diffusion In Ionic Liquids: Parallels With Conventional Solvents A. Kaintz, A. Benesi, G. Baker, M. Maroncelli Design Of Ionic Liquid-Derived Charged Polymers Undergoing LCST-Type Phase Transition With Water Y. Deguchi, Y. Kohno, H. Ohno How A Subsequent Methylation Of The Imidazolium Ring Affects The Therochemical Properties Of Ils S. P. Verevkin, Dz.H. Zaitsau, A. V. Yermalayeu, V. N. Emel’yanenko, R. Ludwig, C. Schick, Y. Zhang, E. J. Maginn The Molecular Structure Of Mixtures Of Ionic Liquids I. J. Villar-Garcia, F. Cameron, J. P. Hallett, T. Welton Liquid-Liquid Phase Splits Induced By CO2 In Mixtures Of Toluene+Ionic Liquid R. Canales, J. F. Brennecke Nanostructure Of Fluorous Protic Ionic Liquids Which Contain Hydrocarbon, Fluorocarbon And Polar Domains T. Greaves, D. Kennedy, Y. Shen, G. Song, C. Drummond Investigation On Surface Structures Of [Cnmim][Otf] Aqueous Solutions Using Nonlinear Vibrational Spectroscopy Y. Sakai, B. Kamalakanta, T. Iwahashi, T. Ishiyama, A. Morita, D. Kim, Y. Ouchi Effect Of Temperature On Quantum Yields Of Solvated Electron By Electron Photodetachment In A Room Temperature Ionic Liquids R. Musat, K. Takahashi, E. Saenko, V. Feldman, R. Crowell Upper Limit Challenge For The Enthalpy Of Vaporization Of Ionic And Molecular Compounds With Quartz Crystal Microbalance D. H. Zaitsau, S. P. Verevkin The Effect Of Polyvalent Cations In The Formation Of Ionic-Liquid-Based Aqueous Biphasic Systems K. Adi Kurnia, M. G. Freire, J. A. P. Coutinho Desulfurization Of Fuel Using Metal Based Ionic Liquids M. Yamin, M. Yacob, K. Adi Kurnia, M. I. Abdul Mutalib ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 33 CONFERENCE REPORTS CO2 Solubility In Switchable Ionic Liquid Based On DBU-Glycerol- CO2 E. Sapei, A. Ostonen, P. Uusi-Kyyny, V. Alopaeus Hydrogen Bonding In Protic Ionic Liquids R. Hayes, S. Imberti, G. G. Warr, R. Atkin Thermodynamic Study On Phase Behaviours Of Amide-Based Ionic Liquids Incorporated With Conformatiol Change K. Fujii, M. Imanari, K. Nishikawa Surface Adsorption Behavior Of Ionic Liquid Aqueous Solutions: Halide Anion Dependence W. Sung, W. Wang, A. Mingqi, N. A. Anderson, D. Vaknin, D. Kim Density Measurement Of CO2/Imidazolium-Based Ionic Liquids Up To 20mpa Using X-Ray Absorption Method S. Okumura, T. Morita, K. Nishikawa Heat Capacity, Excess Molar Volumes And Viscosity Deviation Of Binary Systems Of N-Octylisoquinolinium Bis{Trifluoromethylsulfonyl}Imide Ionic Liquid U. Domanska, M. Zawadzki, M. Królikowski Physical Properties Of Deep Eutectic Solvent And Ionic Liquid Based On Choline And Malonic Acid And Their Aqueous Solutions K. Kobierska, A. Makowska, J. Szydłowski Eutectic Mixtures Of Ionic Liquids M. Smiglak, K. Szubert, H. Maciejewski Deep Eutectic Solvents V. Fischer, W. Kunz Gibbs Adsorption Isotherms Of Mixtures Of Ionic Liquids With Organic Solvents A. Knorr, M. Geppert-Rybczynska, J. Safarov, A. Heintz Thermochemistry Of [HB][A] (A = Cl−, [NO3]−, [O2CCH3]−; B = Mim+, Tmg+) Protic Ionic Liquids J. Vitorino, C. E. S. Bernardes, M. E. Minas Da Piedade Deep Eutectic Solvents Formulation Based On Choline Chloride And Carboxylic Acids D. Gutiérrez-Tauste, E. Torralba-Calleja Physical Properties, Structure, And Interactions Of Ionic Liquids With Alkyl-Phosphonate Anions J. Pitawala, J. Scheers, P. Jacobsson, A. Matic ___________________________________________________________________________ page 34 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ionic Liquids As Hydrotropes: A Study On The Solubility Of Vanillin, Gallic Acid And Caffeine In Aqueous Solutions A. F. M. Cláudio, H. Passos, T. Mourão, M. G. Freire, J. A. P. Coutinho CO2 Capture By Bio-Ionic Liquids P. Sanglard, E. Vanoli Imidazolium-Based Ionic Liquids And Imidazoles: Comparing Properties, Performances And Possibilities J. E. Bara, C. H. Turner, S. P. Verevkin, M. S. Shannon, W. J. Horne, M. S. Hindman, A. C. Irvin, A. Stanton, J. W. Whitley, H. Liu Can Ionic Liquid Mixtures Improve The CO2/N2 Separation Performance Of Supported Liquid Membranes? L. Tomé, D. J. S. Patinha, C. S. R. Freire, L. P. N. Rebelo, I. M. Marrucho Thermophysical Properties And Solvation Of Cholinium Carboxylate Based Ionic Liquids And Water Mixtures D. Patinha, H. Garcia, L. C. Tomé, R. Ferreira, L. P. N. Rebelo, C. S. Pereira, I. M. Marrucho High Ionicity Ionic Liquids (Hiils): Comparing Ethylsulfonate- And Ethylsulfate-Based Ionic Liquids F. S. Oliveira, A. B. Pereiro, J. M. M. Araújo, J. N. Canongia Lopes, G. Feio, S. Todorovic, L. P. N. Rebelo, I. M. Marrucho Physical Properties Of Binary Mixtures Of Ionic Liquids Containing A Common Cation H. F. D. Almeida, M. G. Freire, J. A. P. Coutinho, J. N. Canongia Lopes, I. M. Marrucho, L. P. N. Rebelo Study Of Ions Mobility In [Emim]CH3COO Ionic Liquid By Means Of 13C And 1H NMR Relaxation V. Matveev, D. Markelov, P. Ingman Structural Fluctuation Of Imidazolium-Based Ionic Liquids And Carbon Dioxide Mixtures T. Morita, S. Okumura, K. Nishikawa CO2 Absorption Properties Of Glyme-Lithium Salt Mixtures At 313.15 K D. Kodama, M. Kanakubo, H. Arai, Y. Endo, T. Shimomura, T. Makino, A. Suzuki Lyotropic Liquid-Crystalline Behavior Of Pyridinium-Based Amphiphilic Zwitterions In Protic Ionic Liquids T. Matsumoto, T. Ichikawa, T. Kato, H. Ohno Carbon Dioxide Absorption Properties In Amino-Metallate Ionic Liquids A. E. Rosamilia, H. Liu, J. Huang ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 35 CONFERENCE REPORTS Ionic Liquids Containing Transition Metal Functional Groups For CO2 Capture J. Huang, H. Liu, I. H. J. Arellano, A. E. Rosamilia, A. Warden, P. Pendleton Surface Tension Measurements Of Ammonium Ionic Liquids K. Materna Utilization Of N-Methyl-6-Oxyquinolinium Betaine For Probing Inter- And Intramolecular Interactions In Ionic Liquids S. Schmode, R. Ludwig, N. P. Ernsting Inductive Effect As A Tool To Fine-Tune Ionic Liquids S. Sowmiah, C. A. M. Afonso, J. M. S. S. Esperança, J. N. Canongia Lopes, L. P. N. Rebelo Unusual LCST-Type Behaviour In Mixtures Of Cholinium-Based Ionic Liquids With Ethers A. J. L. Costa, M. R. C. Soromenho, K. Shimizu, J. N. Canongia Lopes, J. M. S. S. Esperança, L. P. N. Rebelo Absorption Of Carbon Dioxide By Ionic Liquids With Carboxylate Anions S. Stevanovic, A. Podgorsek, L. Moura, C. Santini, A. A. H. Pádua, M. C. Gomes Interactions Of Imidazolium Dicyanamide Ionic Liquids With Carbon Nanomaterials J. M. P. França, C. A. Nieto De Castro, A. A. H. Pádua Thermal Conductivity Of Graphene Based Nano And Ionanofluids S. Patil, K. Patil, F. Reis, S. Vieira, S. M. Sohel Murshed, M. J. Lourenço, C. Nieto De Castro Thermodynamics And Volumetric Properties Of {[EMIM][N(CN)2] (1) + An Aromatic, Or Aliphatic Hydrocarbon (2)} Binary Systems M. Królikowski, K. Walczak, U. Domañska Physicochemical And Excess Properties Of {Dicyanamide - Based Ionic Liquid (1) + Water (2)} Binary System M. Królikowska How Pressure And Temperature Affect The Viscosity Of Ionic Liquids. Ils Film Thickness In Lubrication F. M. Gaciño, T. Regueira, M. J. P. Comuñas, L. Lugo, X. Paredes, J. Fernández Volumetric And Compressibility Behaviour Of Twelve Ionic Liquids Up To 120 Mpa T. Regueira, F. M. Gaciño, L. Lugo, M. J. P. Comuñas, J. Fernández Studies On The Dissolution Of Carbohydrates In Ionic Liquids And ___________________________________________________________________________ page 36 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Extraction Using The Antisolvent Method El-S. R. E. Hassan, F. Mutelet, J-C. Moise Physicochemical And Structural Properties Of Ionic Nanofluids Y. U. Paulechka, M. P. Shevelyova, G. J. Kabo, A. V. Blokhin, A. G. Kabo, T. N. Levitskaya N-Donor Functionalised Room Temperature Ionic Liquids: Their ThermoPhysical, Electrochemical And Transport Properties T. Ruether, T. Rodopoulos, M. D. Horne, J-P. Veder, M. Kanakubo, L. A. Woolf, K. R. Harris Transport Properties Of Bis(Trifluoromethylsulfony)Amide (TFSI)-Based Protic Ionic Liquid For Supercapacitor Application L. Timperman, F. Beguin, E. Frackowiak, M. Anouti Ionic Association And Interactions In Ionic Liquid + Water Systems B. E. Mbondo Tsamba, J. M. Andanson, M. F. Costa Gomes, S. Sarraute, M. Traikia, P. Husson Amphiphilic Quaternary Ammonium Carboxylate Ionic Liquids: Physicochemical Properties, Theoretical Modeling And Application To Cellulose Dissolution A. Mühlbauer, F. Boissou, L. Leclercq, K. De Oliveira Vigier, B. Estrine, W. Kunz, F. Jérôme, V. Nardello-Rataj NMR Pulsed Field Gradient Self-Diffusion Study Of Orthoborate Ionic Liquids A. Filippov, F. U. Shah, M. Taher, S. Glavatskih, O. N. Antzutkin Ionic Liquids Based On Diethylmethyl(2-Methoxyethyl)Ammonium (DEME) And Bis(Perfluoroalkanesulfonyl)Amide: Short-And Long Range Structural Features F. Castiglione, O. Russina, Y. Yoshida, A. Triolo, A. Mele Thermophysical Properties Of 1-Ethyl-2-Alkylpyridinium Bis(Trisfluoromethylsulfonyl) Imide Ionic Liquid Series M. A. A. Rocha, A. S. M. C. Rodrigues, M. Vilas, E. Tojo, L. M. N. B. F. Santos Accurate Volatility Study Of 1-Ethyl-2-Alkylpyridinium Bis(Trifluoromethylsulfonyl) Imide Ionic Liquid Series M. A. A. Rocha, A. S. M. C. Rodrigues, M. Vilas, E. Tojo, E. Sapei, L. M. N. B. F. Santos Adsorption Isotherms Of Ionic Liquid Surfactants On Gold Surfaces: Structural Effects M. Tariq, A. P. Serro, B. Saramago, J. N. Canongia Lopes, L. P. N. Rebelo ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 37 CONFERENCE REPORTS Characterizing Structures In Ionic-Liquid Aqueous Solutions Using Volumetric Data M. Tariq, J. M. S. S. Esperança, J. N. Canongia Lopes, L. P. N. Rebelo Fluorinated Ionic Liquids For Efficient Perfluorocarbon Gases Absorption A. Belén Pereiro, J. Palomar, I. M. Marrucho, L. P. N. Rebelo 1,2,3-Triazolium Based Ionic Liquid Crystals K. Stappert, A-V. Mudring 1,3-Dialkylimidazolium Based Ionic Liquid Crystals M. Yang Investigation Of The Side Chain Fluorination Methylimidazolium Ionic Liquids With Varying Anions H. Weber, A. S. Pensado, A. Stark, B. Kirchner On 1-Butyl-3- Molecular Dynamics Simulation Studies Of The Interactions Between Ionic Liquids And Tetraethyleneglycol L. I. N. Tomé, M. G. Freire, J. R. B. Gomes, J. A. P. Coutinho The Fragment Molecular Orbital Approach In Large-Scale Ab Initio Calculations Of Pyrrolidinium And Imidazolium-Based Ionic Liquids J. L. Hodgson, E. I. Izgorodina Microheterogeneities In Dilute Solutions Of Rtils M. Bier, L. Harnau Polarisability In Ionic Liquids C. Schröder, O. Steinhauser Aggregation In Water Of Imidazolium-Based Ionic Liquids Containing Ibuprofenate Anion: A Combined Experimental And Molecular Dynamic Study D. Brevet, B. Coasne, J. M. Devoisselle, M. In, P. Judeinstein, C. TournePeteilh, A. Vioux, L. Viau Molecular Simulation Study Of The Dynamics Of Ionic Liquid (IL) [Bmim][Tf2N] Confined In Graphite Slit Pore S. Budhathoki, J. K. Shah, E. J. Maginn Solvation Dynamics Of Excess Electron In A Room Temperature Ionic Liquid K. Takahashi, R. Musat, T. Kondo, Y. Yoshida, E. Saenko, V. Feldman, R. Crowell, J. Wishart Structure Analyses Of Solvate Ionic Liquids Composed Of Glyme And Alkali Metal Salts T. Mandai, R. Nozawa, K. Yoshida, K. Ueno, K. Dokkko, M. Watanabe ___________________________________________________________________________ page 38 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Dissecting The Interaction Energies In Protic Ionic Liquids K. Fumino, V. Fossog, K. Wittler, R. Hempelmann, R. Ludwig Intermolecular Interactions And Liquid Properties Of Protic Ionic Liquids: Comparison With Aprotic Ionic Liquids S. Tsuzuki, W. Shinoda, S. Miran, H. Kinoshita, T. Yasuda, K. Dokko, M. Watanabe The Origin Of The Long-Range Magnetic Ordering Of The New Magnetic Ionic Liquid 1,3-Dimethylimidazolium Tetrachloroferrate P. Migowski, I. Pedro Del Valle, A. G. Saiz, J. A. B. Rodriguez, J. R. Fernandez, J. Dupont Prediction Of Mutually Immiscible Ionic Liquids By COSMO-RS Method S. S. Legsal, J. Palomar, J. J. Rodríguez New Insights On The Structural Shifts In The [Cnmim][Ntf2] Ionic Liquids Series Using Static Structure Functions And Aggregate Analysis C. E. S. Bernardes, K. Shimizu, J. N. Canongia Lopes First Principle Prediction Of Ionic Liquid Melting Points E. Maginn, Y. Zhang Comparative Study Of The OKE Spectra And Physical Properties Of Branched And Linear Alkyl Chain Imidazolium Ionic Liquids L. Xue, F. Bardak, G. Tamas, E. Gurung, Y. P. Koh, S. L. Simon, E. L. Quitevis Thermodynamic Modeling Of Aqueous Solutions Containing Ionic Liquids. Description Of The Osmotic Coefficients Using The Binding-MSA Model N. Papaiconomou, J-P. Simonin, O. Bernard Extraction From Water Of Metals (Gold, Platinum Or Tungstene) As Anionic Metal Complexes Using Ionic Liquids N. Papaiconomou, S. Genand-Pinaz, I. Billard, J-M. Lévêque, S. Viboud, S. Guittonneau Non-Equilibrium Molecular Simulations Of Ionic Liquid Lubricants At Metallic Surfaces: Prediction Of The Friction A.C. F. Mendonça, P. Malfreyt, A. A. H. Pádua Coarse Grained MD Of An IL-Based Capacitor: Parameter Study On Size, Valency And Shape K. Breitsprecher Analysis Of The Potential Of PC-SAFT Equation Of State To Model Natural Refrigerant + Ionic Liquid Systems M. M. Mato, J. L. Legido, J. Salgado, A. Coronas, J. Garcia Why Some Ils Are Hydrophilic And Some Are Hydrophobic: Meta___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 39 CONFERENCE REPORTS Structure Observed In Ils D. Kun, S. Zhang, Q. Wang, J. Wang Poster Session 2 Synthesis And Characterization Of An Electroactive Based On The Ferrocenylsulfonyl (Trifluoromethylsulfonyl) Imide Anion B. Gélinas, D. Rochefort Design Of Chiral Ionic Liquids: Structural Investigation Towards Chiral Recognition M. Vasiloiu, P. Gaertner, K. Bica Ionic Liquids Tracing Impurities - Change In Properties C. Schmidt, T. Peppel, J. Lehmann, M. Köckerling, U. Kragl Synthesis And Physico-Chemical Characterization Of New PyridiniumBased Dicationic Ionic Liquids M. Mahrova, E. Tojo, A. Igartua Novel Methodologies To Prepare Amino Acid Based Ionic Liquids And Molten Salts Using CO2 And Organic Superbases G. V. S. M. Carrera, M. Nunes Da Ponte, L. C. Branco Indirect Electroreductive Cyclisation Of Unsaturated Halides In Ionic Liquid Medium M. J. Neto, J. M. S. S. Esperança, A. P. Esteves, M. M. Silva, M. J. Medeiros Carvone Derived Ionic Liquids As Chiral Shift Reagents F. Santamarta, Y. Fall, E. Tojo Acido-Basic Ionic Liquids - Characterization And Performance As Acid Catalysts M. Wild, A. Stark Combining Ionic Liquid Catalysts And Microwave Heating To Optimise Clean Methylation Chemistry With Dimethylcarbonate T. Yan, T. N. Glasnov, J. D. Holbrey, C. O. Kappe, K. R. Seddon Room-Temperature Synthesis Of The Bi5[Gacl4]3 Salt From Three Different Classes Of Ionic Liquids J. Åkerstedt, L. Kloo, M. Gorlov Simple Preparation Of Novel Types Of Magnetic Ionic Liquids With Hybrid Type Anion H. Onishi, Y. Kusunoki, Y. Takagi Ionothermal Synthesis Of Chalcogenide Nanomaterials: Copper Indium Selenide (Cuinse2, CIS) ___________________________________________________________________________ page 40 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS S. Tyrrell, P. Nockemann, M. SwadźBa-KwaśNy Metal-Containing Ionic Liquids Straight From The Shelf! F. Coleman, M. SwadźBa-KwaśNy Effect Of Ultrasonic Irradiation On Ionic Liquid Assisted Porous Silica Gel Matrix Y. Lal Verma, R. Kumar Singh Synthesis Of Ionic Liquid Confined Mesoporous Silica Gels: A Low Density Material A. Kumar Gupta, R. Kumar Singh, S. Chandra Coordination Of Indium With Phosphine Oxide Functionalised Ionic Liquids S. Olejarz, M. Swadzba-Kwasny, H. Q. Nimal Gunaratne, P. Nockemann Phosphine Oxide Functionalised Ionic Liquids: Tuneable Ligands For Lanthanide Complexation J. Alvarez Vicente, A. Mlonka, H. Q. Nimal Gunaratne, M. SwadźBa-KwaśNy, P. Nockemann, J. Jacquemin 5-Cyano-Tetrazolate Room Temperature Ionic Liquids - Just A “Click” Away J. Sundermeyer, T. Bergholz, B. Oelkers Synthesis And Properties Of Bio-Based Ionic Liquids Composed Of Choline-Derived Cations And Carboxylate Anions A. Mühlbauer, L. Leclercq, W. Kunz, B. Estrine, V. Nardello-Rataj Recyclable Iron Nanoparticle Catalysts For Selective Hydrogenation Of Alkynes In Ionic Liquids A. Welther, M. T. Keßler, M. H. G. Prechtl, A. Jacobi Von Wangelin Ionic Liquid Modified Zeolites For The Production Of Campholenic Aldehyde And Fencholenic Aldehyde P. Mäki-Arvela, E. Salminen, P. Virtanen, N. Kumar, J-P. Mikkola Novel Amino Acids Based Ionic Liquids As Organocatalysts For Asymmetric Aldol And Michael Reactions K. Zalewska, L. C. Branco Electrospray Ionization Mass Spectrometry For Studying Reactions In Ionic Liquids M. M. Seitkalieva, L. L. Khemchyan, E. A. Khokhlova, V. P. Ananikov Silyl Peroxides As Effective Oxidants In The Baeyer-Villiger Reaction With Chloroaluminate(III) Ionic Liquids As Catalysts A. Chrobok, R. Słupska, S. Baj ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 41 CONFERENCE REPORTS Old Ammonium Salts To New Applications: Transformation Of Carbohydrates To 5-Hydroxymethylfurfural (HMF) S. P. Simeonov, J. A. S. Coelho, C. A. M. Afonso Development Of Novel Ionic Liquids For Tribological Applications G. Tiago, R. Colaço, B. Saramago, L. C. Branco Development Of Biocompatible Ionic Liquids A. Forte, L. C. Branco Experimental And Theoretical Studies On Conversion Of Carbon Dioxide With Epoxides Catalyzed By 2-Hydroxyl-Functionalized Ionic Liquids J. Wang, S. Zhang, W. Cheng, J. Sun Effects Of Ionic Liquids Structure On The Cellulose Dissolution Y. Zhao, X. Liu, S. Zhang, J. Wang An Effective Method For The Glycolysis Of Poly(Ethylene Terephthalate) (PET) Catalyzed By A Metal-Containing Ionic Liquid Q. Wang, X. Lu, S. Zhang, H. Gao Efficient Conversion Of CO2 Into Organic Carbonates Based On AnionCation Cooperative Catalysis Of Ionic Liquids S. Zhang, W. Cheng, J. Sun, J. Wang Introduction Of Third Generation Solvent System: Electro-Reduction Of Organic Molecules O. Abdul-Rahim, T. Ruether, P. Permutter, A. M. Bond CO2 Solubilities In Imidazolium, Ammonium And Pyrrolidinium Ionic Liquids With Bis(Trifluoromethanesulfonyl)Amide Anion T. Makino, M. Kanakubo, T. Umecky, A. Suzuki The Potential Of Halide Electrochemistry In Ionic Liquids For Redox Flow Batteries L. Yu, G. Z. Chen Chelating Ionic Liquids For Reversible Zinc Electrochemistry M. Kar, B. Winther-Jensen, M. Forsyth, D. Macfarlane Solid-State Ion-Selective Electrodes Based On Ionic Liquids That Melt Slightly Above Room Temperature A. V. Rzhevskaia, N. V. Shvedene, V. E. Baulin, I. V. Pletnev Self-Organization Of Functional Ionic Liquids Into Bicontinuous Cubic Liquid-Crystalline Assemblies T. Ichikawa, T. Matsumoto, K. Fujimura, T. Kato, H. Ohno Ultrathin Ionic Liquid Films On Carbon-Based Surfaces ___________________________________________________________________________ page 42 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS F. Rietzler, A. Deyko, F. Maier, H-P. Steinrück Protic Ionic Liquid-Based Anhydrous Proton Conducting Di-Ureasil Hybrid Electrolytes M. A. Cardoso, M. Fernandes, L. C. Rodrigues, M. M. Silva, V. De Zea Bermudez Electrochromic Devices Incorporating Biohybrid Electrolytes Doped With Ionic Liquids M. Fernandes, S. Pereira, E. Fortunato, R. Rego Interaction Of Taf5 And Nbf5 With Two Different Ionic Liquids Containing An Imidazolium- And A Pyrrolidinium Cation S. Krischok, A. Ispas, A. Zühlsdorff, A. Ulbrich, A. Bund, F. Endres Titanium Deposition From Guanidinium- And Imidazolium-Based Ionic Liquids C. Berger, T. Jacob The Electrochemical Interface Of Gold And Silver Single Crystals In Imidazolium-Based Ionic Liquids C. Müller, T. Jacob Can Ionic Liquid Dispersive Liquid-Liquid Microextraction Be Combined With Screen Printed Electrodes As Electrochemical Detectors? E. Fernández, L. Vidal, J. Iniesta, C. E. Banks, A. Canals Electrochemical Characterization Of Cellulose Dissolved In Ionic Liquids Y. Sugano, S. Aldea, A. Ivaska, J-P. Mikkola Halogen Free Boron-Based Ionic Liquids As Novel Lubricants M. Taher, F. Ullah Shah, A. Filippov, S. Glavatskih, O. N. Antzutkin Boundary Films At Metal Oxide-Ionic Liquid Interfaces Studied By SolidState NMR Spectroscopy F. Ullah Shah, S. Glavatskih, O. N. Antzutkin Preparation Of Stable Gold Nanoparticles Using Ionic Liquids T. Ghilardi, C. Chiappe, G. Cevasco Liquid Metal Salts: Ionic Liquids For High Current Density Electroplating Of Copper And Silver S. Schaltin, N. R. Brooks, J. Sniekers, K. Binnemans, J. Fransaer Tuned Imidazolium Based Ionic Liquids For Energy Storage H. Rouault, H. Srour, C. Santini Dysprosium-Based Polymeric Ionic Liquid: A Renewable Catalyst For Multicomponent Reactions At 353 K And A Single Chain Magnet At Low ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 43 CONFERENCE REPORTS Temperatures D. Prodius, F. Macaev, Y. Lan, N. Sucman, G. Buth, V. Mereacre, C. E. Anson, A. K. Powell Comparative Study On Thermophysical Properties Of Two Sulfonium And Ammonium Ionic Liquids: Electrical Energy Storage Application E. Coadou, L. Timperman, J. Jacquemin, C. Hardacre, M. Anouti Thermophysical Properties Of Pyrolidinium Nitrate Protic Ionic Liquid + Propylene Carbonate Binary Mixture J. Pires, L. Timperman, J. Jacquemin, A. Balducci, M. Anouti Electrodeposition Of Indium And Gallium From A Deep Eutectic Solvent For Thin Film Solar Cell Applications J. Malaquias, M. Steichen, P. J. Dale Ionic Liquids: New Multifunctional Agents Of Polymer Matrices L. Sébastien, G. Jean-François Structural And Ionic Transport Behaviour Of Polymeric Gel Based On Polymer Pvdf-HFP And Ionic Liquid [BMIM][BF4] With And Without Lithium Salt S. K. Shalu, R. K. Chaurasia, S. C. Singh An Application For The Full Electrical Car: Ionic Liquids In Lithium Air Battery D. Gutiérrez-Tauste, C. Aucher, E. Knipping, D. Amantia, A. Almarza, L. Aubouy, J. A. Sáez Ionic Liquids As Electrolyte For Mg/Air Batteries S. Jeremias, S. Jeong, V. Siozios, S. Passerini Electrochemical Properties Of Conducting Polymers Electrogenerated In Ionic Liquids L. Ben Aiachia, P. Goujon, T. H. Ho, C. Gabrielli, H. Perrot, M. Turmine Li+ Transport In Ionic Liquid–Organic Carbonate Mixtures R-S. Kühnel, S. Jeremias, S. Menne, S. Passerini, M. Winter, A. Balducci Organic Ionic Plastic Crystal Electrolytes For Lithium (Metal) Batteries P. Howlett, M. Forsyth, D. R. Macfarlane Controlling The Properties Of Energetic Ionic Liquids Through The Incorporation Of Reactive Nanomaterials P. D. Mccrary, S. A. Alaniz, R. D. Rogers Polymer Electrolyte Based On DNA And N,N,N-Trimethyl-N-(2Hydroxyethyl) Ammonium Bis(Trifluoromethylsulfonyl)Imide, [N1 1 1 2(OH)][Ntf2] R. Leones, M. Fernandes, J. M. S. S. Esperança, A. Pawlicka, V. De Zea ___________________________________________________________________________ page 44 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Bermudez, M. M. Silva Analysis And Observation Of Bulk Polymer Properties In AlkylFunctionalized Poly(Ils) W. J. Horne, M. S. Shannon, J. E. Bara, K. Terrill, A. C. Irvin, A. D. Stanton, M. S. Hindman Transparent Bioactive Films Based On Polysaccharides And Ionic Liquids L. C. Tomé, N. H. C. S. Silva, A. J. D. Silvestre, I. M. Marrucho, C. S. R. Freire Ionic Liquids As Adjuvants For The Tailored Extraction Of Caffeine In Aqueous Two- Phase Systems Composed Of 2-Propanol And K3PO4 S. B. Santos, I. A. Oliveira Reis, C. P. C. Silva, J. A. P. Coutinho, M. G. Freire, C. M. Faria Soares, A. S. Lima Ionic Liquid ́s Extraction Of Low Volatility Compounds: The Particular Case Of Opiate Removal From Human Hair Surface J. Restolho, M. Barroso, M. J. Dias, B. Saramago, C. A. M. Afonso Composite Membranes From Epoxide-Functionalized Imidazolium Rtils And Multifunctional Amines: Preparation, Characterization And Gas Permeability W. M. Mcdanel, T. K. Carlisle, A. K. Swanson, M. G. Cowan, D. L. Gin, R. D. Noble Ionic-Liquid Gel Based Carbon Dioxide Gas Sensor M. Honda Fuel Cells Using Protic Ionic Liquids As Proton Conductor T. Yasuda, Y. Honda, J. Wang, M. Watanabe Ionic Liquids - New Lubricants For Wind Power Plants A. Westerholt, A. Bösmann, P. Wasserscheid, W. Arlt, J. Völkl, E. Schlücker, B. Pohrer, W. Holweger, M. Wolf, Y. Korth, N. Wehrum, A. Solano Novel Ionic Liquids For CO2 -Absorption M. Bahlmann, P. Schulz, A. Schraven, P. Schwab, P. Wasserscheid Molecular Hydrogen Storage: Ionic Liquid Supported Thermal Dehydrogenation Of Ethylene Diamine Bisborane And Hydrazine Bisborane S. Sahler, H. Konnerth, L. Heim, N. Knoblauch, M. H. G. Prechtl Development Of New Working Pairs For Absorption Chillers And Sorption Heat Pump Systems Based On Ionic Liquids S. Popp, R. Wölfel, A. Bösmann, P. Wasserscheid, M. C. Schneider, S. Willmes, M. Seiler Encapsulated Ionic Liquids (Enils): From Continuous To Discrete Liquid ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 45 CONFERENCE REPORTS Phase J. Lemus, J. Palomar, N. Alonso-Morales, J. Bedia, M. A. Gilarranz, J. J. Rodríguez Continuous Gas Drying By Absorption In Ionic Liquids F. Heym, M. Krannich, W. Korth, A. Jess Ag+-Bmimbf4 Based Polymer Composite As Facilitated Transport Membranes For Propane/Propylene Separation M. Fallanza, A. Ortiz, D. Gorri, I. Ortiz Optimization Of Salt Extraction Process By A Novel Anodic Reaction B. Khalaghi, L. Teng, S. Seetharaman Removal And Recovery Of Ionic Liquids From Contaminated Water Streams Using Aluminium-Based Salts C. M. S. S. Neves, M. G. Freire, J. A. P. Coutinho Extraction Of Butyric Acid By Solvent Impregnated Resin M. Blahušiak, Š. Schlosser, J. Marták Bis(Trifluoromethylsulphonyl)Imide Ionic Liquids As Lubricants I. Otero, F. López-Sánchez, E. R. López, J. Fernández Ionic Liquids At Aluminium Surfaces A. S. Pensado, A. A. H. Pádua, F. Malberg, X. Paredes, B. Kirchner, J. Fernández Long Term Thermal Stability Of 1-Butyl-2,3-Dimethylimidazolium Based Ionic Liquids. Comparison With Perfluoroalkylpolyethers J. J. Parajó, M. Villanueva, I. Otero, J. Salgado, J. Fernández C CO2 Uptake In Supported Ionic Liquid Phase (SILP) Materials H. Kolding, A. Riisagere, R. Fehrmann Ionic Liquids As Heat Transfer Medium T. J. S. Schubert, H. Sahin, M. Götz, K. Bär, D. Buchholz Ionic Liquids For CO2 Capture T. J. S. Schubert, G. Adamová, B. Iliev, G. Romanos, M. Kroon Metal Recycling In Deep Eutectic Solvents G. Frisch, A. P. Abbott, J. Hartley On The Mechanism Of CO2 Absorption In 1,3-Dialkylimidazolium Acetate Ionic Liquids O. Hollóczki, D. S. Firaha, M. Brehm, R. Cybik, B. Kirchner Separation Of Gaseous Hydrocarbons Using Imidazolium-Based Ionic Liquids ___________________________________________________________________________ page 46 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS L. Moura, V. Bernales, A. A. H. Padua, M. F. Costa Gomes, C. C. Santini Phosphonium Ionic Liquids As Carriers Of Metal Ions From Chloride Solutions In Separation Processes M. Regel-Rosocka, M. Baczynska, M. Wisniewski Selective Treatment Of Oil Distillates Obtained From Baku Oil With Ionic Liquids H. R. Azizbejli, R. V. Aliyeva, R. Z. Hasanova, A. H. Azizov A Multiscale Research Strategy To Develop Gas Separation Process Based On Ionic Liquids J. Palomar Herrero, V. Ferro, N. Alonso, J. Bedia, J. Lemus, M. GonzálezMiquel, E. Ruiz, J. De Riva, C. Moya, M. A. Gilarranz, J. J. Rodriguez Extraction Of Arsenic-Containing Chemical Warfare Agents From Sea Sediment Samples Using Ionic Liquid Solutions U. Hakala, W. Wo, H. Koskela, K. Wähälä, P. Vanninen Development Of Advanced DNA Sensors In The Hydrated Ionic Liquid Of Choline Dihydrogen Phosphate H. Tateishi-Karimata, N. Sugimoto Ruthenium-Ionanofluid: Density, Viscosity And Thermal Conductivity Studies V. Patil, D. Salavera, C. Rode, A. Coronas Light Olefin/Paraffin Separation Using Polymeric Ionic Liquid Membranes Containing Ag+-IL As Carrier L. Tomé, D. Mecerreyes, C. S. R. Freire, L. P. N. Rebelo, I. M. Marrucho Extraction Of Tetracycline From Fermentation Broth Using Aqueous Biphasic Systems Composed Of Polyethylene Glycol And Cholinium-Based Ionic Liquids J. F. B. Pereira, F. Vicente, V. C. Santos-Ebinuma, J. M. Araújo, A. Pessoa Jr., M. G. Freire, J. A. P. Coutinho Neodymium Extraction Using Salt Extraction Process A. Abbasalizadeh, L. Teng, S. Seetharaman A New Method For The Conversion Of Cellulose To Glucose Using Hydrophobic Ionic Liquids In The Presence Of Licl A. Kamimura, M. Yoshimoto Salicylate Ionic Liquids: Pharmacokinetic And Toxicity In Vitro Assays P. C. A. G. Pinto, V. D. Justina, S. P. F. Costa, S. Reis, K. Bica, M. L. M. F. S. Saraiva An Enzymatic Biofuel Cell Using Hydrophobic Ionic Liquids As ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 47 CONFERENCE REPORTS Electrolytes M. Masuda, N. Nakamura, H. Ohno Catalytic Conversion Of Biomass-Derived Carbohydrates Into Γ Valerolactone In Ionic Liquids D. Paolicchi, A. Riisager Ionic Liquids In Biosensors: Influence Of Hydrated Choline Based Ils On The Bio-Functionality Of Lactate Oxidase V. Curto, S. Scheuermann, V. Ranganathan, D. R. Macfarlane, D. Diamond, F. Benito-Lopez Effect Of Ionic Liquids On The Survival And Embryonic Development Of The Freshwater Snail Biomphalaria Glabrata D. R. A. Souza, C. M. Melo, R. R. Madi, A. S. Lima, V. L. S. Jeraldo “Direct” And Reverse Ionic Liquids Micelles M. M. Pereira, L. D. F. Santos, S. P. M. Ventura, A. S. Lima, J. A. P. Coutinho Dissolution Of Cellulose Obtained Morpholium Based Ionic Liquid Brines D. Raut, W. Qing Su, J-P. Mikkola From Different Processes In Competitive Immunoassay For Progesterone In Ionic Liquid Media P. C. A. G. Pinto, K. Dourado, M. L. M. F. S. Saraiva Ionic Liquids For Active Ingredient Isolation From Biomass: A Greener Approach For Drug Synthesis A. K. Ressmann, P. Gaertner, K. Bica Distillable Superbase-Derived Acid-Base Conjugate Ionic Liquids For Biomass Processing A. Parviainen, A. W. T. King, I. Mutikainen, C. Selg, I. Kilpeläinen Transdermal Pharmacokinetic Studies Of Ionic Liquids Composed Entirely Of Active Pharmaceutical Ingredients K. R. Di Bona, D. Yancey, S. Rizvi, M. Gray, G. Gurau, J. L. Shamshina, J. F. Rasco, R. D. Rogers Fungal Viability In Choline-Based Ionic Liquids A. G. Santos, B. Dias Ribeiro, D. Sales Alviano, M. A. Zarur Coelho Development Of Recyclable Ionic Liquids For Biomass Processing A. W. T. King, A. Parviainen, A. J. Holding, I. Mutikainen, I. Kilpeläinen Prodrug Ionic Liquids: Functionalizing Neutral Active Pharmaceutical Ingredients To Take Advantage Of The Ionic Liquid Form O. A. Cojocaru, J. Shamshina, K. Bica, G. Gurau, A. Narita, P. D. Mccrary, P. S. Barber, R. D. Rogers ___________________________________________________________________________ page 48 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Development And Biological Evaluation Of API-Ils Based On AntiBacterial And Anti- Fungal Drugs R. Ferraz, L. C. Branco, R. Fernandes, C. Prudêncio, J. P. Noronha, Ž. Petrovski Dissolution Of Keratin In Ionic Liquids A. Idris, R. Vijayaraghavan, U. Ali Rana, A. F. Patti, D. R. Macfarlane Ecotoxicity Of Technological Relevant Ionic Liquid Anions S. Steudte, P. Stepnowski, S. Stolte Hazard Assessment Of Dicationic Ionic Liquids P. Stepnowski, S. Steudte, S. Stolte Studies On The Extraction And Regeneration Of Cellulose From Miscanthus Using Ionic Liquids El-Sayed R. E. Hassan, F. Mutelet, J-C. Moise Ionic Liquids As Tools For Controlling Gene Expression In Model Filamentous Fungi C. Silva Pereira New Insights In The Extraction Mechanism Of Suberin By Cholinium Hexanoate R. Ferreira, H. Garcia, A. Sousa, C. Freire, A. Silvestre, W. Kunz, L. P. N. Rebelo, C. Silva Pereira Extraction Of A Hydrophobic Biopolymer With Cholinium Based Ionic Liquids H. Garcia, R. Ferreira, C. Martins, A. Sousa, C. Freire, A. Silvestre, W. Kunz, L. P. N. Rebelo, C. Silva Pereira Omics Approaches To Explore Ionic Liquids Stress In Filamentous Fungi P. C. Alves, D. O. Hartmann, I. Martins, H. Garcia, M. C. Leitão, J. Berker, L. P. N. Rebelo, C. Silva Pereira Ionic Liquids As Extracting Phases For Nanoparticles: Consequences On The Toxicity Of Aqueous Phases S. Viboud, N. Papaiconomou, C. Payrard, D. Fontvieille Synthesis And Characterization Of Active Pharmaceutical Ingredients Containing Ionic Liquids C. D. Wilfred, F. J. Romeli New Ionic Liquids From Renewable Resources S. Sowmiah, C. A. M. Afonso, J. M. S. S Esperança, L. P. N Rebelo Environmental Impact Of Pyridinium, Pyrrolidinium And AmmoniumBased Ionic Liquids Y. Deng, P. Besse-Hoggan, M. F. Costa Gomes, A. M. Delort, M. Sancelme, P. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 49 CONFERENCE REPORTS Husson Designing Ionic Liquids For Increased Lipase Activity F. J. Deive, D. Ruivo, J. M. S. S. Esperança, L. P. N. Rebelo, M. Ángeles Sanromán, A. Rodríguez Changes In Α-Amylase Stability And Activity Induced By Ionic Liquids D. Ruivo, M. A. Cardoso, P. M. Reis, V. De Zea Bermudez, F. J. Deive, A. Rodriguez, J. M. S. S. Esperança, L. P. N. Rebelo Extraction Of Antioxidants From Microalgae With Ionic Liquids M. S. Álvarez, M. Tariq, I. Teijiz, F. Moscoso, M. Sánchez, J. Sineiro, J. M. S. S. Esperança, L. P. N. Rebelo, A. Rodríguez, F. J. Deive, M. Ángeles Sanromán Cetylpyridinium Salicylate For Coating Of Implants: Characterization And Application J. Bandomir, F. Stein, S. Petersen, K. Sternberg, U. Kragl Synthesis, On The Stability Of Imidazolium-Based Ionic Liquids: The Bulk And The Gas Phase F. Malberg, O. Hollóczki, C. Dreßler, A. S. Pensado, B. Kirchner Extraction Of 5-Hydroxymethylfurfural Understanding Molecular Interactions A. Stark, D. H. Zaitsau, S. Verevkin From Ionic Liquids: Vaporisation And Thermal Decomposition Of Halide Ion Ionic Liquids K. R. J. Lovelock, J. P. Armstrong, P. Licence, R. G. Jones Determination Of CO2 Concentration And The Diffusion Coefficient In EMIM Ntf2 By FTIR Measurement B. Pohrer, K. Kortenbruck, E. Schlücker Effect Of Temperature And Hydrogen Bonding Degree On Several Properties Of Ammonium Nitrate-Based Ionic Liquids And Their Mixtures With Lithium Salts J. R. Rodríguez, S. Bouzón-Capelo, T. Méndez-Morales, J. Carrete, O. Cabeza, J. Vila, E. López-Lago, M. Turmine, L. M. Varela Investigation Of Imidazolium Based Aprotic Heterocyclic Anion (AHA) Ionic Liquids Using NMR M. A. Desilva, S. Seo, C. Shi, M. Massel, J. F. Brennecke Solubility Behaviour Of 1-[(1R,2S,5R)-(—)-Menthoxymethyl]-3Alkylimidazolium Ntf2 Chiral Ionic Liquids A. Andresová, J. Feder-Kubis, Z.Wagner, J. Jacquemin, M. Bendová Olefin-Paraffin Separation Using Task-Specific Materials Based On Ionic Liquids ___________________________________________________________________________ page 50 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS J. Jacquemin, Y. Wang, J. Zhou, J. Thompson, N. G. Shie Ling, M. Atilhan, M. Khraisheh, D. Rooney Crystallization Behaviour In The System EMIM-Cl/BMIM-Cl/H2O M. Kick, P. Keil, A. König Decomposition Kinetics Of Thermally Stressed Ionic Liquids M. Kick, P. Keil, A. König Effect Of Water In Phosphonium Based Ionic Liquid C. Pozo-Gonzalo, M. Forsyth, P. Howlett Effect Of Liquid-Crystalline/Isotropic Phase Transitions On The Ionic Liquid Surface By Means Of ARXPS T. Matsuda, I. Niedermaier, F. Kohler, M. Müller, P. Wasserscheid, H-P. Steinrück, F. Maier Activity Coefficients At Infinite Dilution For Organic Solutes And Water In 1-Butyl-4-Methylpyridinium Dicyanamide, [Bmpy][N(CN)2] M. Królikowski, M. Królikowska, U. DomańSka Phase Equilibria Study Of (Ionic Liquid + Water) Binary Mixtures M. Królikowska, M. Karpiñska Study Of Thermochromic Effect In Newly Synthesized 1-(2-Hydroxyethyl)3- Methylimidazolium Nitrate Ionic Liquid S. Dozic, M. Vranes, S. Gadzuric Volumetric Properties Of Binary Mixtures Of 1-Butyl-1Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide With Polar Organic Solvents M. Vranes, S. Dozic, S. Gadzuric Liquid–Liquid Equilibria And COSMO-RS Modeling Of Ternary Systems Composed Of Ionic Liquid, 1-Hexanethiol And N-Dodecane A. R. Ferreira, M. G. Freire, L. A. Neves, J. C. Ribeiro, F. M. Lopes, J. G. Crespo, J. A. P. Coutinho Lead(II) Chloride Ionic Liquids And Organic/Inorganic Hybrid Materials – A Study Of Chloroplumbate(II) Speciation G. Feng, R. W. Murphy, P. Nockemann, K. R. Seddon, M. Swadzba-Kwasny, F. Coleman Probing Structure And Nano-Segregation In Rtils - 129Xe NMR And MD Simulations P. Morgado, K. Shimizu, J. M. S. S. Esperança, E. J. M. Filipe, J. N. Canongia Lopes Thermophysical Properties Of Ionic Liquids At High Temperatures And Pressures ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 51 CONFERENCE REPORTS R. Hamidova, J. Safarov, I. Kul, A. Shahverdiyev, E. Hassel Vapor Pressure Of Ionic Liquid 1-Hexyl-3-Methylimidazolium Bis(Triflluoromethylsulfonyl)Imide With Methanol Or Ethanol R. Hamidova, J. Safarov, I. Kul, A. Shahverdiyev, E. Hassel Self-Aggregation Of Ionic Liquids Based On Di-NAlkyldimethylammonium Cation: A Dual Behaviour Between Hydrotropes And Surfactants L. Leclercq, A. Mülbauer, V. Nardello-Rataj Gas Phase Affinity Scales For Ions Typical Of Ionic Liquids J. Vitorino, J. P. Leal, M. E. Minas Da Piedade Hydrogen Bonding In Alkylammonium Nitrate Ionic Liquids S. Mukhopadhyay, N. V. Plechkova, S. Rudic, K. R. Seddon, S.-M. Stana, J. Tomkinson Langmuir Films Of Ionic Liquids: Mono And Multilayering Of [Octadecylmim][Ntf2] And [Octadecylmim][Cl] At The Air-Water Interface C. Maia, P. Morgado, M. Rosamonte, M. Goldmann, J.-B. Sarrazin, J. N. Canongia Lopes, E. J. M. Filipe Probing The Role Of Cation And Anion Structure In The Intermolecular Dynamics Of Ionic Liquids Through OKE Spectroscopy E. L. Quitevis, F. Bardak, L. Xue, G. Tamas Trihexyl(Tetradecyl)Phosphonium Ionic Liquids As Surfactants For Enhanced Oil Recovery: Phase Behaviour And Physical Properties S. Lago, A. Soto, A. Arce Influence Of Nanoparticle Concentration On The Physical Properties Of Agi/[P6,6,6,14]Cl Ionanofluids I. Rodríguez-Palmeiro, B. Rodríguez-Cabo, A. Arce Jr., E. Rodil, J. M. SáizJabardo, A. Soto Combined Physical-Chemical Absorption Of CO2 In A Mixture Of Ionic Liquids A. M. Pinto, H. Rodríguez, A. Soto, A. Arce High Thermal Stability And Low Viscosity Ionic Liquids In Aromatic Extraction P. N. Tejedor, M. L. Martínez, J. G. González, F. R. Somolinos Liquid-Liquid Extraction Of Toluene From C6 - C8 Aliphatic Hydrocarbons Using 1-Alkyl-3-Methylimidazolium Dicyanamide Ionic Liquids M. Larriba Martínez, P. Navarro Tejedor, J. García González, F. Rodríguez Somolinos ___________________________________________________________________________ page 52 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Thermophysical Properties Of Ionic Liquids: The Role Of The -CN Group M. G. Freire, C. M. S. S. Neves, J. A. P. Coutinho, I. M. Marrucho, J. N. Canongia Lopes, L. P. N. Rebelo Self-Aggregation In Ionic-Liquid-Based Aqueous Biphasic Systems And Its Impact In The Extraction Of Alkaloids H. Passos, M. P. Trindade, T. S. M. Vaz, J. A. P. Coutinho, M. G. Freire Measurement Of Vapor-Liquid Equilibria For [C4mim][SCN], [C4mim][N(CN)2], [C4mim][C(CN)3] And [C4mim][B(CN)4] With Water And Ethanol I. Khan, P. J. Carvalho, L. M. N. B. F. Santos, J. A. P. Coutinho NMR Investigation Of Chemical Reactions Of CO2 In 1-Butyl-3Methylimidazolium Acetate Ionic Liquid F. Vaca Chávez, M. Besnard, I. Cabaço, P. J. Sebastião, J. A. P. Coutinho, J. Mascetti, Y. Danten Deep Eutectic Solvents – Choline Chloride And Polyols Mixtures R. J. B. N. Santos, H. F. D. Almeida, G. J. Maximo, A. J. Meirelles, M. G. Freire, J. A. P. Coutinho A Computational Study On The Interactions Within Binary Systems Of CN-Based Ionic Liquids With Water And Ethanol M. L. S. Batista, J. R. B. Gomes, J. A. P. Coutinho Thermal Stability Of Ionic Liquids Derived From Imidazolium And Choline Cations J. Salgado, M. Villanueva, E. Tojo, P. Verdia, M. Vilas, J. Garcia Non-Covalent Interactions In Imidazolium Based Ionic Liquids R. P. Matthews, P. A. Hunt Physical And Mechanical Properties Of Phosphonium Based Poly(Ionic Liquids) K. J. Fraser, A. Kavanagh, B. Ziolkowski, S. Gallagher, D. Diamond Specific Behaviour Of Reichardt ́S Betaine Dye In Binary Mixtures Of Tetrabutylammonium Glycine And Tetrabutylammonium L-Alanine With Molecular Solvents A. R. Harifi-Mood, M. Ghanbarnejad Solubility Of Iso-Butane In 1-Alkyl-3-Methylimidazolium Bis[(Trifluoromethyl)Sulfonyl] Imide Ionic Liquids L. Pison, M. C. Gomes On The Influence Of CO2 On Carbene Formation Dialkylimidazolium Acetate Ionic Liquids D. S. Firaha, O. Hollóczki, M. Brehm, R. Cybik, B. Kirchner In 1,3- ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 53 CONFERENCE REPORTS N- To Iso-Alkylisomerization Effect On The Thermophysical Properties Of Ionic Liquids A. S. M. C. Rodrigues, M. A. A. Rocha, H. F. D. Almeida, M. G. Freire, J. A. P. Coutinho, L. M. N. B. F. Santos Separation Of Phenols In Aqueous Two-Phase System K. Materna Magnetic Resonance Investigations Of Ion-Solute Interactions In Ionic Liquids S. Khatun, M. F. Thomas, E. W. Castner Jr Carbon Dioxide Gas Hydrate Formation In Aqueous Solution Of Ionic Liquid: 1-Aminopyl-3-Methylimidazolium Bromide K. Guo, Y. Bi, C. Yang Solubility And Phase Behaviour Of Binary Systems Containing CholineDerived Salts J. Lopes, M. E. Zakrzewska, A. V. M. Nunes, C. A. M. Afonso, A. A. Rosatella, N. T. Lourenço, A. M. R. Rocha, M. N. Da Ponte, V. Najdanovic-Visak Calorimetric Study Of Polymorphism Bis(Trifluoromethanesulfonyl)Imide Ionic Liquids Y. U. Paulechka, A. V. Blokhin, G. J. Kabo In A Study Of The Structural Evolution In Ionogels By In Situ SAXS-Mraman Spectroscopy M. Nayeri, A. Martinelli Effect Of Water On Structure And Physicochemical Properties Of Ionic Liquids N. Yaghini, A. Martinelli, J. Pitawala, L. A. Medina, A. Matic Rheology Of Ionic Liquids And Ionanofluids F. J. V. Santos, A. P. Ribeiro, J. França, F. Pimentel, S. Molias, C. A. Nieto De Castro Thermophysical Properties Of Dca Ionanofluids F. Reis, J. França, F. J. V. Santos, S. M. S. Murshed, M. J. Lourenço, C. A. Nieto De Castro Thermophysical Properties Of Dca Ionic Liquids S. Molias, F. Reis, J. França, F. Santos, M. J. Lourenço, C. Nieto De Castro Ionic Liquids: Determination Of Thermodynamic Properties Didecyldimethylammonium Salts Using Inverse Gas Chromatography J. ZiemblińSka, P. Bielecki, W. Wasiak Of ___________________________________________________________________________ page 54 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ultraslow Dynamics At Crystallization Of Methylimidazolium-Based Ionic Liquids K. Nishikawa, H. Seki, M. Imanari Cold Crystallization Behavior Of Co-Existed Water Molecules Observed In Dihydrogen Phosphate Analogs K. Fujita, Y. Nikawa, H. Ohno Influence Of Phosphate-Based Salts On The Formation Of Aqueous Biphasic Systems With Ionic Liquids T. Mourão, A. F. M. Cláudio, I. Boal-Palheiros, M. G. Freire, J. A. P. Coutinho Ionic-Liquid-Based Aqueous Biphasic Systems As A New Approach To Separate Maltodextrins S. F. Carvalho, L. P. N. Rebelo, J. A. P. Coutinho, I. Boal-Palheiros, M. G. Freire Surface Tension Of Ionic Liquids: Anion, Cation And Water Content Effects H. F. D. Almeida, J. A. Lopes-Da-Silva, M. G. Freire, J. A. P. Coutinho The Cation Symmetry Effect On The Surface Tension Of Bis[(Trifluoromethyl)Sulfonyl] Imide-Based Ionic Liquids H. F. D. Almeida, M. G. Freire, J. A. Lopes-Da-Silva, A. M. Ferndandes, M. A. A. Rocha, L. M. N. B. F. Santos, J. A. P. Coutinho Hydrogen-Bonding And The Dissolution Mechanism Of Uracil In An Acetate Ionic Liquid: Insights From NMR Spectroscopy And Quantum Chemical Calculations J. M. M. Araújo, A. B. Pereiro, J. N. Canongia Lopes, L. P. N. Rebelo, I. M. Marrucho Liquid-Liquid Equilibria Of Perfluorocompounds With Fluorinated Ionic Liquids S. Martinho, J. M. M. Araújo, L. P. N. Rebelo, I. M. Marrucho, A. B. Pereiro Perspectives On Fluorinated Ionic Liquids: Properties And Applications A. B. Pereiro, S. Martinho, J. M. M. Araújo, S. Nunes, A. Matias, C. M. M. Duarte, L. P. N. Rebelo, I. M. Marrucho A Comparative Study Of The Solid-Fluid Transitions Of Hmim (Pfbu)SO3 And NB4 (Pfbu)SO3: New Fluorinated Domain A. B. Pereiro, M. J. Pastoriza-Gallego, K. Shimizu, I. M. Marrucho, J. N. Canongia Lopes, M. M. Piñeiro, L. P. N. Rebelo Ionic Liquids Based Aqueous Biphasic Systems: Effect Of The Alkyl Chains In The Cation Versus In The Anion D. Patinha, F. Alves, L. P. N. Rebelo, I. M. Marrucho High Ionicity Ionic Liquids (Hiils): Insights Into The Interactions Between Ionic Liquids And Inorganic Salts With Common Ions ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 55 CONFERENCE REPORTS F. S. Oliveira, E. J. Cabrita, S. Todorovic, L. P. N. Rebelo, I. M. Marrucho Hydrogen Bonding Influence On The Phase Behaviour Of Mixtures Of Ionic Liquids And Molecular Solvents A. J. L. Costa, P. Papis, P. M. Reis, K. Shimizu, J. Szydłowski, J. N. Canongia Lopes, J. M. S. S. Esperança, L. P. N. Rebelo Phase Behaviour Of Cholinium-Based Bistriflimide Ionic Liquids + Alcohols A. J. L. Costa, M. R. C. Soromenho, K. Shimizu, J. N. Canongia Lopes, J. M. S. S. Esperança, L. P. N. Rebelo Temperature Of Maximum Density (TMD) Of Ionic Liquid Aqueous Solutions M. Tariq, J. M. S. S. Esperança, M. R. C. Soromenho, L. P. N. Rebelo, J. N. Canongia Lopes Evidence Of Viscosity Minima In Binary (Ionic Liquid + Molecular Solvent) Systems M. Tariq, J. M. S. S. Esperança, J. N. Canongia Lopes, L. P. N. Rebelo Deep Eutectic Solvents Based On Choline Chloride And Carboxylic Acids C. Florindo, F. S. Oliveira, L. P. N. Rebelo, I. M. Marrucho Miscibility Of Ammonium-Based Bis(Trifluoromethylsulfonyl)Imide Ionic Liquids With Diols P. Papis, J. Szydłowski, J. M. S. S. Esperança, J. N. Canongia Lopes, L. P. N. Rebelo Ionic Liquids Under Tension H. Veiga, M. R. C. Soromenho, J. M. S. S. Esperança, J. N. Canongia Lopes, L. P. N. Rebelo One Or Two Side Chains: The Nano-Structures Of Di-Alkyl And MonoAlkyl Bistriflamide Ionic Liquids K. Shimizu, C. E. S. Bernardes, L. M. N. B. F. Santos, J. N. Canongia Lopes Modeling Solubility Of Carbohydrates In Ionic Liquids Using The PCSAFT Equation Of State A. Carneiro, C. Held, O. Rodríguez, E. Macedo, G. Sadowski Room Temperature Ionic Liquids With Fluorinated Tails: Evidences Of Triphilic Behaviour And Structural Implications A. Triolo, O. Russina, F. Lo Celso, S. Passerini, B. G. Appetecchi, A. Mele, R. Caminiti, F. Castiglione Uncovering Molecular Secrets Of Ionic Liquids By Computational Approaches S. Zahn ___________________________________________________________________________ page 56 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Peudolattice Theory Of The Electrical Conductivity Of Mixtures Of Ionic Liquids And Molecular Solvents L. M. Varela, T. Méndez-Morales, J. Carrete, O. Cabeza, L. J. Gallego Cations With Polar Tails And The Role Of Anions In The X-Ray Scattering Of Ils C. J. Margulis, H. K. Kashyap, R. P. Daly, J. Hettige, H. V. R. Annapureddy Computational Study Of The Formation Of Stable Clusters In Mixtures Of Lithium/Sodium Salts With Ionic Liquids T. Méndez-Morales, J. Carrete, M. Pérez-Rodríguez, O. Cabeza, L. J. Gallego, L. M. Varela Computer-Aided Molecular Design Of Ionic Liquids: Prediction Of Melting Point D. C. Weis, D. R. Macfarlane Novel Strategy For Low Viscosity Of Ionic Liquids By Anion Stabilisation Through Intra-Anionic Hydrogen Bonding A. E. Rosamilia, J. Huang Capturing The Influence Of Zn (II) Ions On Anhydrous [Emim][Tf2N] Ionic Liquid For CO2 Absorption Using Ppc-SAFT H. Liu, J. Huang, I. H. J. Arellano, A. Warden, P. Pendleton Heterogeneous Systems Containing Ionic Liquids: Interactions With Metal Surfaces And Carbon Nanomaterials A. S. Pensado, A. Podgorsek, A. C. F. Mendonça, J. M. P. França, A. A. H. Pádua Structure Of The Electrical Double Layer In Room Temperature Ionic Liquids - Insigths From Computer Simulations N. Georgi Understanding The Competitive Influence Of Dispersive Interactions And H-Bonding In Structuring Imidazolium Based Lonic Liquids P. Hunt, R. P. Matthews Simulation Studies Of Dynamic Properties In An Organic Ionic Plastic Crystal [P1224]+[PF6]F. Chen, L. Jin, S. W. De Leeuw, P. Howlett, J. M. Pringle, M. Forsyth Extraction Of Tryptophan With Ionic Liquids: A Molecular Simulation Study A. Seduraman, M. Klähn Ab Initio Prediction Of Proton NMR Chemical Shifts In ImidazoliumBased Ionic Liquids S. Chen, D. R. Macfarlane, E. I. Izgorodina First Principles Approaches To Studying Ionic Liquids E. I. Izgorodina, J. Rigby, J. L. Hodgson, S. Tan ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 57 CONFERENCE REPORTS Insights Into The Physical Nature Of Interactions In Ionic Liquids From Quantum Chemical Calculations B. Szefczyk, G. Hantal, W. A. Sokalski Design Of Ionic Liquids With High CO2/CH4 Selectivity For Gas Sweetening Applications Using COSMO-RS K. A. Kurnia, J. A. P. Coutinho Separation Of Benzene From N-Octane: A Quantum Chemical Approach K. A. Kurnia, M. I. A. Mutalib Mechanisms Of Toxicity Of Ionic Liquids: A Microscopic And Molecular Approach D. O. Hartmann, M. Petkovic, L. P. N. Rebelo, C. S. Pereira Back Extraction Of Gallic Acid Using Aqueous Two-Phase Systems Composed Of Ionic Liquids A. F. M. Cláudio, C. F. C. Marques, L. Boal-Palheiros, M. G.Freire, J. A. P. Coutinho Closing session Application Of Ionic Liquids In Biological Processes: Enzymatic Reactions, Molecular Dynamic Simulation Of Enzyme, And Protein Refolding (PL11) N. Lan Mai, S-W. Bae, H. Shin Kim, Y-M. Koo Closing Remarks - L. P. N. Rebelo, J. N. Canongia Lopes ___________________________________________________________________________ page 58 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS 223rd ECS Meeting May 12-17, 2013 • Toronto, Canada Behavior of Nickel in KF-2HF Molten Salt: An Electrochemical Study – Adam Fajner and Brian Ikeda An Inorganic Molten Salt Supercapacitor – Donald W. Kirk and John W. Graydon Ionic Liquids – Co-Chairs: Paul C. Trulove and Robert A. Mantz A Reference Electrode for Room Temperature Ionic Liquids Electrochemical Studies – Boris Shvartsev, Hila Shasha, Eliezer Gileadi, Ruediger Eichel, and Yair EinEli Influence of Electrode Potential On the Interfacial Structure of Cleaved Single Crystal Bi(111) Electrode 1-Butyl-4-Methylpyridinium Tetrafluoroborate Interface – Erik Anderson, Vitali Grozovski, Liis Siinor, Carolin Siimenson, Vladislav Ivaništšev, Karmen Lust, and Enn Lust Solvation: Why Lithium Trifluoromethanesulfonate in Common Battery Solvents Makes a Poor Electrolyte – Matthew P. Foley, Christopher J. Worosz, Luke M. Haverhals, Kurt D. Sweely, Wesley Henderson, Hugh De Long, and Paul C. Trulove Co-Chairs: T. Richard Jow and Pu Chen Towards New Battery Electrolytes – Hassan Srour, Helene Rouault, and Catherine Santini The Effect of Water Addition On Zn/Zn(II) Redox Reactions in Bis(Trifluoromethanesulfonyl)Imide Based Room Temperature Ionic Liquids Min Xu, Douglas G. Ivey, and Zhong Xie, and Wei Qu Optimizing the Electrochemical Performance of Imidazolium-Based Polymeric Ionic Liquids by Varying Tethering Groups ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 59 CONFERENCE REPORTS – Zhe Jia Comparison of Two Ionic Liquids as the Supporting Electrolytes of NonAqueous Redox Flow Battery – Dapeng Zhang andYongdan Li Lithium Electrolyte Based on Quaternary Ammonium Ionic Liquids for High Voltage Lithium Batteries – LE My Loan Phung Electrodeposition and Electrodissolution of Aluminum in Ionic Liquid Electrolytes Meng-Chang Lin, Jeng-Kuei Chang, Chun-Hsing Wu, Yi-Cheng Lee, Yu-Li Lin, and Chang-Chung Yang Nano/Bio Sensors Co-Chairs: Zoraida Aguilar, Hugh De Long, Ajit Khosla, L. A. Nagahara, Aleksandr Simonian, and Nianqiang Wu The Effect of Ionic Liquid (BMIM-BF4) on Screen-Printed Glucose Irc Biosensor Modified with Crosslinking Chitosan Matrix – Chang-Jung (Alan) Hsueh, Enoch Nagelli, Liming Dai, and Chung-Chiun Liu Green Electrodeposition – CU, ZN and CU-ZN Alloys Electrodeposition From Ionic Liquids –Patrick Fricoteaux, Celine Rousse, and Sylvie Beaufils Electrodeposition of Niobium on Magnesium Using Green Ionic Liquids – Anil Mahapatro and Jehanzeb Hakim Ion Conduction in Polymers Co-Chair: Thomas A. Zawodzinski Ionic-Liquid Gel Based Carbon Dioxide Gas Sensor Masahito Honda, Yusuke Takei, Koutaro Ishizu, Hiroshi Imamoto , Kiyoshi Matsumoto, Isao Shimoyama ,and Toshihiro Itoh, and Ryutaro Maeda Innovations and New Directionsin Organic Electrochemistry Co-Chairs: Graham T. Cheek and Siegfried R. Waldvogel ___________________________________________________________________________ page 60 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Development of Triarylamine Mediator Having Ionic-Tag and Its Application to Electrocatalytic Reaction in Ionic Liquid – Toshio Fuchigami and Shinsuke Inagi Electrochemical Engineering for the 21st Century: 3 Electrolyte-Electrode Interface and Si Deposition in Ionic Liquid – Jason Komadina, Takahiro Akiyoshi, Yoko Ishibashi, Yasuhiro Fukunaka , Piero Pianetta, and Takayuki Homma poster session Electrodeposition of Zinc Nanoparticles in Anodic Aluminium Oxide from Ionic Liquids – Maksim Starykevich, Yulia Nazarkina, and Aleksey Lisenkov, Mikhail Zheludkevich, and Mario Ferreira Electrodeposition in Ionic Liquids of Metal Oxides for Electrochemical Systems – Michal Tulodziecki , Jean-Marie Tarascon,Pierre-Louis Taberna , and Claude Guery ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 61 March 2013 PUBLICATIONS ___________________________________________________________________________ You publish a lot ... …but not everyone knows about it ! If you want them publicized … send references of your recent papers to: molten.salts@polytech.univ-mrs.fr ___________________________________________________________________________ page 62 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Morphology and electrochemical performance Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode materials treated in molten salts Journal of Power Sources, 241, 2013, 186-195 S.J. Shi, J.P. Tu, Y.Y. Tang, X.Y. Liu, X.Y. Zhao, X.L. Wang, C.D. Gu of Cube-like and plate-like Li[Li0.2Mn0.54Ni0.13Co0.13]O2 particles are obtained after treated in LiCl and KCl molten salts at 800 °C, respectively, comparing to the ball-like original particles calcined in air. The oxide treated in KCl molten salt with large specific area of 17.05 m2 g−1 delivers high discharge capacities of 254.1 mAh g−1 and 168.5 mAh g−1 at current densities of 200 mA g−1 and 2000 mA g−1, respectively. In addition, enhanced cycle stability with capacity retention of 94.9% after 80 cycles at charge–discharge current densities of 200 mA g−1 is obtained for the oxide treated in LiCl molten salt with sacrifice of a little capacity. Such electrochemical performance change is proved to be independent of Li+ diffusion coefficient. It appears that the treatment in molten salts can effectively reform the electrochemical performances of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode materials for various applications. Calcium–bismuth electrodes for large-scale energy storage (liquid metal batteries) Journal of Power Sources, 241, 2013, 239-248 Hojong Kim, Dane A. Boysen, Takanari Ouchi, Donald R. Sadoway Calcium is an attractive electrode material for use in grid-scale electrochemical energy storage due to its low electronegativity, earth abundance, and low cost. The feasibility of combining a liquid Ca–Bi positive electrode with a molten salt electrolyte for use in liquid metal batteries at 500–700 °C was investigated. Exhibiting excellent reversibility up to current densities of 200 mA cm−2, the calcium–bismuth liquid alloy system is a promising positive electrode candidate for liquid metal batteries. The measurement of low self-discharge current suggests that the solubility of calcium metal in molten salt electrolytes can be sufficiently suppressed to yield high coulombic efficiencies >98%. The mechanisms giving rise to Ca–Bi electrode overpotentials were investigated in terms of associated charge transfer and mass transport resistances. The formation of low density Ca11Bi10 intermetallics at the electrode–electrolyte interface limited the calcium deposition rate capability of the electrodes; however, the co-deposition of barium into bismuth from barium-containing molten salts suppressed Ca–Bi intermetallic formation thereby improving the discharge capacity. A dual function of high performance counter-electrode for stable quasisolid-state dye-sensitized solar cells Journal of Power Sources, 241, 2013, 373-378 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 63 PUBLICATIONS Yaoming Xiao, Jihuai Wu, Jeng-Yu Lin, Gentian Yue, Jianming Lin, Miaoliang Huang, Zhang Lan, Leqing Fan A dual function polymer hybrid material poly(3,4-ethylenedioxythiophene) (PEDOT)–poly(acrylic acid) (PAA)–poly(styrenesulfonate) (PSS) was fabricated both as a counter electrode (CE) for I3− reduction and for storage of the liquid electrolyte in quasi-solid-state dye-sensitized solar cells (QS-DSSCs). To enhance the electrocatalytic activity of the nano-PEDOT CE and to improve the ionic conductivity of the three-dimensional (3D) PAA–PSS network, the columnar PEDOT was electropolymerized through the 3D PAA–PSS network. The QS-DSSC showed a high photovoltaic conversion efficiency of 6.35% under full sunlight illumination (100 mW cm−2, AM1.5 G), which reduced to 6.03% after 100 days, indicating this QS-DSSC had a relatively good long-term stability. Evaluation and analysis of Li-air battery using ether-functionalized ionic liquid Journal of Power Sources, 240, 15 October 2013, 14-17 Shougo Higashi, Yuichi Kato, Kensuke Takechi, Hirofumi Nakamoto, Fuminori Mizuno, Hidetaka Nishikoori, Hideki Iba, Takahiko Asaoka Li-air battery using ionic liquids, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) amide (DEME-TFSA) and N-methylN-propylpiperidinium bis(trifluoromethanesulfonyl)amide (PP13-TFSA), as the solvents for electrolyte have been studied. A significant improvement of discharge capacity has been observed for DEME-TFSA (4315 mAh g−1electrode at current density of 0.1 mA cm−2), compared with PP13-TFSA. As a discharged product, aggregates reaching 4 µm diameter in size are formed on the surface of cathode, almost 80% of the products are decomposed after charge. By using Raman spectroscopy, two typical peaks attributed to Li2O2 were detected from the discharged aggregates. From the cross sectional SEM images, vacancy occupation ratios of discharged and charged electrodes are estimated, and they are in good agreement with the theoretical calculations. The discharged products formed inside of the cathode are not decomposed completely by charge. Heat treatment of electrospun Polyvinylidene fluoride fibrous membrane separators for rechargeable lithium-ion batteries Journal of Power Sources, 240, 15 October 2013, 204-211 Yinzheng Liang, Sichen Cheng, Jianmeng Zhao, Changhuan Zhang, Shiyuan Sun, Nanting Zhou, Yiping Qiu, Xiangwu Zhang Polyvinylidene fluoride (PVDF) fibrous membranes for use as lithium-ion battery separators were prepared by electrospinning technique. Heat treatment ___________________________________________________________________________ page 64 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS was introduced to improve the tensile strength and elongation-at-break as well as the tensile modulus of PVDF fibrous membranes, with the best mechanical properties achieved after treatment at 160 °C for 2 h. After heat treatment at 160 °C for 2 h, the ionic conductivity of the liquid electrolyte-soaked PVDF fibrous membranes was 1.35 × 10−3 S cm−1 at room temperature. Moreover, compared with commercial Celgard 2400 separator, heat-treated PVDF fibrous membranes exhibited higher electrochemical stability window and lower interfacial resistance with lithium electrode. In addition, at a 0.2C rate, Li/LiFePO4 cells using heat-treated PVDF fibrous membrane separator showed high charge/discharge capacities and stable cycle performance. Aggregation of nanoparticles in aqueous solutions of ionic liquids Journal of Molecular Liquids, 186, October 2013, 1-6 Hossein Sajjadi, Ali Modaressi, Pierre Magri, Urszula Domańska, Michèle Sindt, Jean-Luc Mieloszynski, Fabrice Mutelet, Marek Rogalski In this work we were concerned with interactions between ionic liquids (IL) and nanoparticles (NPs) dispersed in aqueous solutions leading to the formation of NP clusters of finite size. The NPs used were Al2O3 (d = 80 nm), TiO2 (d < 100 nm), and Fe3O4 (d < 100 nm). ILs were 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) and 1-methacryloyloxypropyl-3-methylimidazolium bromide, [mcpmim][Br]. The latter compound was a new IL synthesized in our laboratory. It was demonstrated that ILs actively participate in the formation of NP aggregates suspended in aqueous solution filling the inter-particle space. The aggregates saturated with IL were used as extractors making it possible for the elimination of compounds dissolved in water. Results of the extraction of anthracene and salicylic acid from aqueous solutions were presented. Thermodynamic studies of ionic interactions in aqueous solutions of Nbutyl-pyridinium bromide at 298.15 K Journal of Molecular Liquids, 186, October 2013, 14-22 Vasim R. Shaikh, Santosh S. Terdale, Gaurav R. Gupta, Dilip G. Hundiwale, Kesharsingh J. Patil Density and osmotic coefficient measurements for aqueous solutions of N-butylpyridinium bromide [Bpy][Br] in concentration range ~ 0.019 to ~ 0.39 mol·kg− 1 at 298.15 K are reported. The density data are used to obtain apparent molar (ϕV), partial molar of solute and solvent respectively as well the limiting partial molar of the solute [Bpy][Br] (by appropriate extrapolation). The experimental osmotic coefficient (ϕ) data are used to determine the activity and mean ionic activity coefficients of solute and solvent respectively. Experimental activity coefficient data are compared with those obtained from Debye–Hückel and Pitzer models. The activity data have been further processed to obtain the ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 65 PUBLICATIONS Gibbs free energy change due to mixing (ΔGm) and excess Gibbs free energy change (ΔGE). The aggregation number (n) and critical micelle concentration (cmc) are obtained for ionic salt in solution phase by applying pseudo-phase separation model to ϕ and ϕV data respectively. Application of McMillan– Mayer theory of solutions to the data is made. The results have been interpreted on the basis of structural characteristic of salt, ion–solvent and ion–ion interactions. Improved electrochemical performance of LiMO2 (M=Mn, Ni, Co)– Li2MnO3 cathode materials in ionic liquid-based electrolyte Journal of Power Sources, 239, 2013, 490-495 Jie Li, Sangsik Jeong, Richard Kloepsch, Martin Winter, Stefano Passerini Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in N-butyl-Nmethylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (1:9 in molar ratio) is successfully tested as electrolyte for the high voltage LiMO2–Li2MnO3 (cathode)/lithium (anode) cells at elevated temperature (40 °C). Compared to conventional electrolytes, such as 1 M LiPF6 solution in the mixed solvent of ethylene and dimethyl carbonate (EC:DMC = 1:1), the use of PYR14FSI–LiTFSI electrolyte results in a net improvement of LiMO2–Li2MnO3 cycling stability while granting comparable initial capacity. In addition, the ionic conductivity of the ionic liquid-based electrolyte at 40 °C is high enough to sustain the excellent rate capability of this cathode material. Li/LiMO2–Li2MnO3 cells delivered initial capacity exceeding 200 mA h g−1 at high current rate (2 C) while retaining 94% of the initial capacity after 100 cycles. Differential capacity versus potential analysis and post-mortem characterization by scanning electron microscope, X-ray diffraction and were carried out to explain the improved performance of LiMO2–Li2MnO3 in the IL-based electrolyte. In search of an appropriate ionic liquid as electrolyte for macroporous manganese oxide film electrochemistry Journal of Power Sources, 239, 2013, 1-8 Tânia M. Benedetti, Vinicius R. Gonçales, Susana I. Córdoba de Torresi, Roberto M. Torresi Macroporous manganese oxide films were produced via template-assisted electrodeposition methodology employing polystyrene spheres with different diameters as template, thereby producing films with different pore sizes. The obtained films were true casts of the template(s) employed, as evidenced by Field Emission Scanning Electron Microscopy. The influence of pore size on capacitive behavior was assessed by cyclic voltammetry experiments in conventional propylene carbonate/LiClO4. Besides the influence of pore size, four different ionic liquids (ILs) were studied as electrolytes, showing that the ___________________________________________________________________________ page 66 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS physico–chemical nature of IL strongly affects the capacitive behavior of macroporous manganese oxide films, particularly in terms of stability throughout successive charge/discharge cycles. Optimal performance was obtained using 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ([BMMI][Tf2N]), in which a constant increase in capacitance was observed for the first 700 charge/discharge cycles. This capacitance remained constant, at least until the 1,000 cycle, and was higher than the capacitance achieved using conventional organic solvents. Moreover, the electrochemical window obtained using [BMMI][Tf2N] was widened (from 0.9 V to 1.5 V), corresponding to a significant gain (up to 75%) in terms of energy density. Thus, the development of electrochemical capacitors may significantly benefit from macroporous manganese oxide film electrochemistry employing ionic liquids as electrolytes. NaFSA–C1C3pyrFSA ionic liquids for sodium secondary battery operating over a wide temperature range Journal of Power Sources, 238, 2013, 296-300 Changsheng Ding, Toshiyuki Nohira, Keisuke Kuroda, Rika Hagiwara, Atsushi Fukunaga, Shoichiro Sakai, Koji Nitta, Shinji Inazawa The physicochemical properties of NaFSA–C1C3pyrFSA ionic liquids were investigated to explore their potential as new electrolytes for sodium secondary batteries operating over a wide temperature range. The viscosity and ionic conductivity of NaFSA–C1C3pyrFSA with a molar ratio of 2:8 were 16.7 cP and 15.6 mS cm−1, respectively, at 353 K. The electrochemical window of this ionic liquid was 5.2 V at 353 K with sodium metal deposition determining the cathode limit. A Na/NaFSA–C1C3pyrFSA/NaCrO2 cell exhibited stable charge– discharge behaviour at 298 and 353 K. The discharge capacities of 92 and 106 mAh (g-NaCrO2)−1 were observed at 298 and 353 K, respectively, at 20 mA g−1. The Coulombic efficiency was higher than 99% during the charge– discharge tests except for the initial few cycles. The cell also showed high discharge rates, reaching 500 mA g−1 at 353 K. Design and parametrization analysis of a reduced-order electrochemical model of graphite/LiFePO4 cells for SOC/SOH estimation Journal of Power Sources, 237, 2013, 310-324 James Marcicki, Marcello Canova, A. Terrence Conlisk, Giorgio Rizzoni The design of predictive, electrochemical, Li-ion battery models and the use of model-order reduction techniques to extract low-order models enables researchers to address problems related to model-based control, estimation, aging, and life-cycle prediction. This paper presents a novel approach to the design and parametrization of a reduced-order model characterizing the dynamic ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 67 PUBLICATIONS voltage response of a Li-ion cell. The model is based on the assumption of uniform active material utilization and includes prediction of the ionic concentration and potential dynamics in the liquid phase, which significantly affects the voltage response for high currents. A model-order reduction procedure based on the Pade approximation method is used to reduce the partial differential equation model to a low-order system of ordinary differential equations. Systematic methods are proposed to identify the electrochemical parameters that govern power and capacity prediction, as well as their temperature dependence. The procedure is based on carefully designed experiments that isolate the influence of small groups of parameters on the voltage output, utilizing complete cell data for model identification almost entirely in place of half-cell characterization. Finally, an extensive validation with experimental data illustrates the ability of the model to accurately predict the cell voltage. Bicyclic imidazolium ionic liquids as potential electrolytes for rechargeable lithium ion batteries Journal of Power Sources, 237, 2013, 5-12 Xiao-Guang Sun, Chen Liao, Nan Shao, Jason R. Bell, Bingkun Guo, Huimin Luo, De-en Jiang, Sheng Dai A bicyclic imidazolium ionic liquids, 1-ethyl-2,3-trimethyleneimidazolium bis(tri fluoromethane sulfonyl)imide ([ETMIm][TFSI]), and reference imidazolium compounds, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([EMIm][TFSI]) and 1, 2-dimethyl-3-butylimidazolium bis(trifluoromethane sulfonyl)imide ([DMBIm][TFSI]), were synthesized and investigated as solvents for lithium ion batteries. Although the alkylation at the C-2 position of the imidazolium ring does not affect the thermal stability of the ionic liquids, the stereochemical structure of the molecules has shown profound influences on the electrochemical properties of the corresponding ionic liquids. [ETMIm][TFSI] has better reduction stability than both [EMIm][TFSI] and [DMBIm][TFSI], as confirmed by both linear sweep voltammetry (LSV) and theoretical calculation. Also, a relatively stable solid electrolyte interphase (SEI) is formed in [ETMIm][TFSI], suggested by the time dependence of the impedance spectra of the Li||Li cell. Furthermore, the Li||graphite half-cell based on [BTMIm][TFSI] exhibits reversible capacity of 250 mA h g−1 and 70 mA h g−1 at 25 °C, which increases to 330 mA h g−1 and 250 mA h g−1 at 50 °C, under the current rate of C/20 and C/10, respectively. For comparison, the halfcell based on [DMBIm][TFSI] exhibits poor capacity retention under the same current rates at both temperatures. N-Alkyl-N-methylpyrrolidinium difluoro(oxalato)borate Physical/electrochemical properties and Al corrosion Journal of Power Sources, 237, 2013, 104-111 ionic liquids: ___________________________________________________________________________ page 68 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Joshua L. Allen, Dennis W. McOwen, Samuel A. Delp, Eric T. Fox, James S. Dickmann, Sang-Don Han, Zin-Bin Zhou, T. Richard Jow, Wesley A. Henderson The synthesis and physical properties of difluoro(oxalato)borate (DFOB−)-based ionic liquids (ILs) are reported with N-alkyl-N-methylpyrrolidinium cations with butyl, pentyl and hexyl alkyl chains. The PY14DFOB and PY16DFOB salts have a melting point (Tm) of −5 °C and 31 °C, respectively, whereas the PY15DFOB salt does not crystallize. Instead, this salt has a glass transition temperature (Tg) of −74 °C. Electrolytes composed of these ILs are noncorrosive toward Al when mixed with LiTFSI and LiFSI, as well as with LiPF6 or LiDFOB. The exceptional oxidative stability of these ILs suggests that they may be suitable for battery electrolyte applications. Li-doped mixtures of alkoxy-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide and organic carbonates as safe liquid electrolytes for lithium batteries Journal of Power Sources, 237, 2013, 204-209 I. Quinzeni, S. Ferrari, E. Quartarone, C. Tomasi, M. Fagnoni, P. Mustarelli The availability of safer electrolytes is an important target in the development of the new lithium batteries. The use of Li-doped mixtures based on ionic liquids and organic carbonates seems to be a very promising approach, because it allows to balance the non-flammability, high conductivity, low viscosity and good electrochemical stability. Here, we reported on the characterization of electrolytes solutions based on Nmethoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (PYR1,2O1TFSI), EC/DEC binary system and LiTFSI, as potential safe electrolytes for lithium batteries. The mixtures were studied in terms of flammability tests, thermal features, physical properties, namely conductivity and viscosity, and electrochemical performances. We also carried out a comparison with the pure IL–Li salt system as well as with the standard electrolyte 1.0 M LiPF6 EC–DEC. The best solution showed ionic conductivity exceeding 7 mS cm−1 at 20 °C, room temperature viscosity lower of about 25 cPs and an overall electrochemical window of 4.5 V. With respect to the pure LiTFSI–IL electrolyte, a very stable interface with Li anode was also observed in at least for 20 storage days. This mixture was tested in a LiFePO4-based cell, and showed good performances at 1 C, assuring electrochemical stability for about 250 cycles with ∼100% efficiency. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 69 PUBLICATIONS Electrochemical and structural investigation of NaCrO2 as a positive electrode for sodium secondary battery using inorganic ionic liquid NaFSA–KFSA Journal of Power Sources, 237, 2013, 52-57 Chih-Yao Chen, Kazuhiko Matsumoto, Toshiyuki Nohira, Rika Hagiwara, Atsushi Fukunaga, Shoichiro Sakai, Koji Nitta, Shinji Inazawa The electrochemical performance of NaCrO2 as a positive electrode material for an intermediate-temperature sodium secondary battery was evaluated in an inorganic ionic liquid, NaFSA–KFSA (FSA = bis(fluorosulfonyl)amide), at 363 K. The positive electrode using NaCrO2, acetylene black, and polytetrafluoroethylene exhibited a stable discharge capacity of 113 mA h g−1 at a current density of 125 mA g−1. The Coulombic efficiency and the capacity retention at the 100th cycle were 99.6% and 98.5%, respectively. Even at the very high current density of 2000 mA g−1, the discharge capacity was maintained at 63 mA h g−1. X-ray diffraction analyses revealed that the deintercalation of Na+ ion from NaCrO2 was associated with several phase transitions in the following sequence: rhombohedral O3, monoclinic O′3, and monoclinic P′3. Thermodynamic studies on Sn–Na alloy in an intermediate temperature ionic liquid NaFSA–KFSA at 363 K Journal of Power Sources, 237, 2013, 98-103 Takayuki Yamamoto, Toshiyuki Nohira, Rika Hagiwara, Atsushi Fukunaga, Shoichiro Sakai, Koji Nitta, Shinji Inazawa The equilibrium potentials for Sn–Na alloy formation reactions are investigated in an intermediate temperature ionic liquid, NaFSA–KFSA (xNaFSA = 0.56, xKFSA = 0.44, FSA = bis(fluorosulfonyl)amides), at 363 K. Galvanostatic intermittent titration technique (GITT) is employed to obtain the potential–Na composition curve of the Sn–Na alloy. Ex situ X-ray diffraction (XRD) analysis reveals that plateaus at 0.16 and 0.08 V vs. Na+/Na in the potential–Na composition curve correspond to α-NaSn/Na9Sn4 and Na9Sn4/Na15Sn4 two-phase states, respectively. Although distinct potential plateaus are not observed, the equilibrium potentials of β-Sn/NaSn2 and NaSn2/α-NaSn are suggested to be 0.53 and 0.46 V vs. Na+/Na, respectively. Finally, the Gibbs free energies of formation of the Sn–Na alloys are calculated and compared with reported data. Density and surface tension of pure ionic liquid 1-butyl-3-methylimidazolium L-lactate and its binary mixture with alcohol and water The Journal of Chemical Thermodynamics, 64, September 2013, 1-13 Haichao Jiang, Ying Zhao, Jianying Wang, Fengyun Zhao, Runjing Liu, Yongqi Hu ___________________________________________________________________________ page 70 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS The density and surface tension of the pure ionic liquid 1-butyl-3-methylimidazolium l-lactate were measured from T (293.15 to 343.15) K. The coefficient of thermal expansion, molecular volume, standard entropy, lattice energy, surface entropy, surface enthalpy, and enthalpy of vaporization were calculated from the experimental values. Density and surface tension were also determined for binary mixtures of {1-butyl-3-methyl-imidazolium llactate + water/alcohol (methanol, ethanol, and 1-butanol)} systems over the whole composition range from T (298.15 to 318.15) K at atmospheric pressure. The partial molar volume, excess partial molar and apparent molar of the component IL and alcohol/water in the binary mixtures were discussed as well as limiting properties at infinite dilution and the thermal expansion coefficients of the four binary mixtures. The surface properties of the four binary mixtures were also discussed. Surface tensions of binary mixtures of ionic liquids with bis(trifluoromethylsulfonyl)imide as the common anion The Journal of Chemical Thermodynamics, 64, September 2013, 22-27 M.B. Oliveira, M. Domínguez-Pérez, O. Cabeza, J.A. Lopes-da-Silva, M.G. Freire, J.A.P. Coutinho While values for thermophysical properties of ionic liquids are becoming widely available, data for ionic liquid mixtures are still scarce. In an effort to overcome this limitation and understand the behavior of ionic liquid mixtures, novel data for the surface tension of mixtures composed of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C4mim][NTf2], with other ionic liquids with a common anion, namely 1-butyl-2,3-dimethylimidazolium, [C4C1mim]+, 3methyl-1-propylpyridinium, [C3mpy]+, 1-methyl-1-propylpyrrolidinium, + [C3mpyr] , and 1-methyl-1-propylpiperidinium, [C3mpip]+, were measured at T = 298.2 K and atmospheric pressure over the entire composition range. From the surface tension deviations derived from the experimental results, it was possible to infer that the cation alkyl chain length of the second ionic liquid constituting the mixture has a stronger influence in the ideal mixture behavior than the type of family the ionic liquid cation belongs to. The Gibbs adsorption isotherms, estimated from the experimental values, show that the composition of the vapor–liquid interface is not the same as that of the bulk and that the interface is richer in the ionic liquid with the lowest surface tension, [C4mim][NTf2]. Sorption of trifluoromethane in zeolites and ionic liquid The Journal of Chemical Thermodynamics, 64, September 2013, 40-49 Mark B. Shiflett, David R. Corbin, Beth A. Elliott, A. Yokozeki Sorption isotherms for trifluoromethane (R-23) on three zeolites, Na-Y, K,H-Y, and Rb,Na-Y and ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [emim][Tf2N] have been measured at ca. 298 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 71 PUBLICATIONS and 323 K, using a gravimetric microbalance. The adsorption on the zeolites reaches about 3 mol · kg−1 at 0.025 MPa and 298 K while in the ionic liquid the absorption reaches 3 mol · kg−1 at about 2.5 MPa (100 times higher pressure). Three different adsorption models (Langmuir, multi-site Langmuir, and BET equations) have been used to analyze the zeolite sorption data, with a particular interest in the heat of adsorption (−ΔH). The heat of adsorption for zeolites NaY, K,H-Y, and Rb,Na-Y were about 35 ± 3 kJ · mol−1, 29 ± 3 kJ · mol−1, and 34 ± 5 kJ · mol−1, respectively. These values are within the range of typical physical adsorption. According to the IUPAC classification, the zeolites exhibit Type II adsorption and according to the Scott and van Konynenburg classification the ionic liquid is predicted to be Type V phase behavior. The adsorption process on the zeolites took more time than the absorption process in the ionic liquid to reach the thermodynamic equilibrium and both processes were reversible. Effect of ionic liquid on the solvation behavior of nonaqueous N,N′salicylidenephenylediamine Schiff base (Salophen) solutions at 298.15 K The Journal of Chemical Thermodynamics, 64, September 2013, 58-64 Hemayat Shekaari, Rasoul Elhami-Kalvanagh, Abolfazl Bezaatpour Thermodynamic properties of N,N′-salicylidenephenylediamine Schiff base (Salophen) in the solutions of ionic liquid, 1-butyl-3-methylimidazolium bromide ([BMIm]Br) + organic solvents (N,N-dimethylacetamide DMA, and dimethylsulfoxide DMSO) have been measured at 298.15 K. The measured density and viscosity values have been used to calculate apparent molar volumes, , standard partial molar volumes, , standard partial molar volumes of transfer, , viscosity B-coefficients, and solvation numbers, , for the solutions being studied. All of these parameters were used to interpret the solute–solvent interactions and solvation process occurring between ionic liquid and Salophen. (Liquid + liquid) equilibria of perfluorocarbons with fluorinated ionic liquids The Journal of Chemical Thermodynamics, 64, September 2013, 71-79 S. Martinho, J.M.M. Araújo, L.P.N. Rebelo, A.B. Pereiro, I.M. Marrucho In order to evaluate the feasibility of partially replace perfluorocarbons (PFCs) with fluorinated ionic liquids (FILs) in PFCs-in-water emulsions, usually used for biomedical purposes, herein the (liquid + liquid) phase equilibria of FILs containing fluorinated chains longer than four carbons with PFCs were carried out in a wide range of temperatures. With this goal in mind, two PFCs (perfluorooctane and perfluorodecalin) were selected and the (liquid + liquid) equilibria of the binary mixtures of these PFCs and FILs were studied at atmospheric pressure in a temperature range from T (293.15 to 343.15) K. For these studies, FILs containing ammonium, pyridinium and imidazolium cations ___________________________________________________________________________ page 72 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS and different anions with fluorocarbon alkyl chains between 4 and 8 were included. Additionally, Non-Random Two Liquid (NRTL) thermodynamic model was successfully applied to correlate the behaviour of the PFCs + FILs binary mixtures. Moreover, thermodynamic functions that describe the solvation process were calculated from the experimental data. Transport and thermal properties of quaternary phosphonium ionic liquids and IoNanofluids The Journal of Chemical Thermodynamics, 64, September 2013, 80-92 A.G.M. Ferreira, P.N. Simões, A.F. Ferreira, M.A. Fonseca, M.S.A. Oliveira, A.S.M. Trino The transport and thermal properties of phosphonium ionic liquids (ILs) and thermally stable suspensions of phosphonium ILs and multiwalled carbon nanotubes (MWCNT) were determined. The thermal conductivity was measured over the temperature range T = (280 to 360) K, and at atmospheric pressure, using the transient hot-wire method with an accuracy estimated as 5% from (0.2 to 2) W · m−1 · K−1 and less than ±0.01 W · m−1K−1 from (0.02 to 0.2) W · m−1 · K−1. The phosphonium ILs studied were trihexyltetradecylphosphonium phosphinate [(C6)3PC14)][Phosph], tretrabutylmethylphosphonium methylsulfate, [(C4)3PC1)] [C1SO4], trihexyltetradecyl phosphonium bis(trifluoromethylsulfonyl)imide, [(C6)3PC14] [NTf2], and trihexyltetradecylphosphonium trispentafluoroeth yltrifluorophosphate [(C6)3PC14][FAP]. For all ILs studied, the thermal conductivities were found to lie within the range (0.12 to 0.16) W · m−1 · K−1. Our measurements combined with selected values from the open literature allowed us to determine a linear increase of combined properties (thermal conductivity, density and molar mass) with the increasing of molar mass. The addition of only (0.1 to 0.2) wt.% of MWCNT to ILs (IoNanofluids) revealed a slight increasing of the thermal conductivity from 0.5% to 1%. There was also observed a slight decrease of the thermal conductivity with increasing temperature for the ILs alone and respective IoNanofluids. The rheological behaviour of [(C6)3PC14)][Phosph], and of [(C6)3PC14][NTf2] based IoNanofluids was evaluated at T = (298.15 to 333.15) K and for shear rates in the range = (3 to 30) s−1. All the samples showed shear thinning behaviour. The thermal stability of the IoNanofluids compared to that of ILs alone was studied by High Resolution Thermogravimetric Analysis. It was found that pure [(C6)3PC14)][Phosph] is a thermally stable IL, whose thermal decomposition under the conditions of this study (2 K · min−1) and starts above T = 513 K. It exhibits a one step thermogravimetric profile ([(C6)3PC14][NTf2] that was already investigated in a previous study). A small shift towards lower temperatures was observed in the thermogravimetric curves of IoNanofluids compared to those of the respective ILs alone indicating comparable thermal stabilities. The heat capacities determined by Modulated Differential Scanning ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 73 PUBLICATIONS Calorimetry within a temperature interval ranging from ca. (310 to 515) K with an estimated uncertainty of less than ±0.012 J · K−1 · g−1. Conductometric study of binary systems based on ionic liquids and acetonitrile in a wide concentration range Electrochimica Acta, 105, 30 2013, 188-199 Oleg N. Kalugin, Iuliia V. Voroshylova, Anastasiia V. Riabchunova, Elena V. Lukinova, Vitaly V. Chaban Although a few groups have recently published transport properties for extensive sets of imidazolium- and pyridinium-based room-temperature ionic liquids (RTILs) and their solutions, there are still no prediction techniques for the conductivity maximum in these systems. We contribute to the discussion by reporting own conductometric data and establishing implicit empirical correlations between ionic structure, concentration and temperature. Our analysis is based on binary systems containing ionic (RTIL) and molecular (acetonitrile) co-solvent. The molar fraction of RTIL in each system ranges from 0 to 50% whereas temperature ranges from 278.15 to 328.15 K. Imidazoliumbased RTILs are sampled by 1-ethyl-3-methylimidazolium, 1-butyl-3methylimidazolium and 1-hexyl-3-methylimidazolium tetrafluoroborates, 1-nbutyl-3-methylimidazolium trifluoromethanesulfonate, and 1-butyl-3methylimidazolium bromide. 1-butyl-4-methylpyridinium tetrafluoroborate is employed to distinguish a role of aromatic ring. Ionic association in all RTIL– AN systems poorly correlates with the cation structure, although strongly depends on the anion size and structure. Cation and anion of RTILs form the ‘contact ion pairs’ (CIPs) where anion is coordinated by imidazole and pyridine rings. Notably, all binary systems exhibit conductivity maximum between χ(RTIL) = 10 and 20%. This maximum slightly shifts towards smaller χ(RTIL), as counterion gets larger. Smaller cations and anions lead to substantial conductivity growth. Conductivity maximum can be boosted and observed at larger χ(RTIL) even at insignificant temperature increase. Our observations provide novel insights into a complicated functional dependence of ionic conductivity versus ionic concentration and temperature. The results may be of extensive practical application, particularly for construction of high-performance electrolyte systems. Developments in electrode materials and electrolytes for aluminium–air batteries Journal of Power Sources, 236, 2013, 293-310 D.R. Egan, C. Ponce de León, R.J.K. Wood, R.L. Jones, K.R. Stokes, F.C. Walsh ___________________________________________________________________________ page 74 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Aluminium–air cells are high-energy density (<400 W h kg−1) primary batteries developed in the 1960s. This review shows the influence of the materials, including: aluminium alloy, oxygen reduction catalyst and electrolyte type, in the battery performance. Two issues are considered: (a) the parasitic corrosion of aluminium at open-circuit potential and under discharge, due to the reduction of water on the anode and (b) the formation of a passive hydroxide layer on aluminium, which inhibits dissolution and shifts its potential to positive values. To overcome these two issues, super-pure (99.999 wt%) aluminium alloyed with traces of Mg, Sn, In and Ga are used to inhibit corrosion or to break down the passive hydroxide layer. Since high-purity aluminium alloys are expensive, an alternative approach is to add inhibitors or additives directly into the electrolyte. The effectiveness of binary and ternary alloys and the addition of different electrolyte additives are evaluated. Novel methods to overcome the selfcorrosion problem include using anionic membranes and gel electrolytes or alternative solvents, such as alcohols or ionic liquids, to replace aqueous solutions. The air cathode is also considered and future opportunities and directions for the development of aluminium–air cells are highlighted. Beneficial influence of succinic anhydride as electrolyte additive on the selfdischarge of 5 V LiNi0.4Mn1.6O4 cathodes Journal of Power Sources, 236, 2013, 39-46 Vasily Tarnopolskiy, Julian Kalhoff, Martina Nádherná, Dominic Bresser, Lionel Picard, Frédéric Fabre, Marlène Rey, Stefano Passerini The self-discharge mechanism of LiNi0.4Mn1.6O4, investigated by electrochemical methods, is mostly attributed to oxidative electrolyte decomposition due to the high lithium (de-)insertion potentials, since the material insertion capacity appears to be fully reversible upon subsequent galvanostatic cycling. A series of 40 different compounds, such as for instance fluorinated ethylene carbonate, 1,3-propane sultone, lithium bis(oxalato)borate (LiBOB), or a variety of ionic liquids, was investigated as suitable electrolyte additives to form a stable LNMO/electrolyte interphase in order to prevent the self-discharge by the continuous oxidative electrolyte decomposition. Among these, only one compound, namely succinic anhydride, revealed to have a beneficial effect on the self-discharge of LNMO based cathodes, while showing an enhanced coulombic efficiency and a decreased capacity loss per cycle. Additionally, the modification of the LNMO particles surface by adding succinic anhydride to the electrolyte was confirmed by performing ex situ SEM and XPS analysis of galvanostatically cycled electrodes. N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide-based organic electrolyte for high performance lithium–sulfur batteries Journal of Power Sources, 236, 2013, 207-214 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 75 PUBLICATIONS Lina Wang, Hye Ryung Byon Development of lithium–sulfur (Li–S) batteries has suffered from insufficient capacity and poor cycle-life. One of the reasons for these drawbacks is loss of active material, which is associated with the rapid diffusion of highly soluble lithium polysulfides formed as intermediates of discharge products in organic electrolytes, resulting in internal shuttling of lithium polysulfides. The diffusion of lithium polysulfides is determined largely by the physicochemical properties of electrolytes. Therefore, design of the physicochemical properties of the electrolyte to restrain the internal shuttling is vital to promote high performance for Li–S batteries. Here we present a newly designed room temperature ionic liquid (RTIL)-based organic electrolyte for Li–S battery. Our electrolyte provides a trade-off between solubility and diffusion rate of lithium polysulfides by mixing very different physicochemical properties of two solvents: high lithium polysulfide solubility of 1,2-dimethoxyethane (DME), and high viscosity of N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13TFSI). An adequate composition ratio of mixed PP13-TFSI/DME afforded large capacity, high Coulombic efficiency, improved capacity retention, and suppressed internal shuttling. Electrochemical behavior of anodically obtained titania nanotubes in organic carbonate and ionic liquid based Li ion containing electrolytes Electrochimica Acta, 104, 2013, 228-235 S. Ivanov, L. Cheng, H. Wulfmeier, D. Albrecht, H. Fritze, A. Bund Amorphous and anatase TiO2 nanotube layers were synthesized by means of Ti foil anodic oxidation performed in ethylene glycol based electrolyte containing fluoride ions. A typical surface structure of TiO2 nanotubular layer, well aligned nanotubes with inner diameter of 70–100 nm and wall thickness of about 10– 15 nm was obtained. Both amorphous and converted to anatase nanotube layers were mechanically stable and well adherent to the Ti current collector. The nanostructured Ti/TiO2 layers were tested as a current collector – anode material system for Li-ion intercallation in 1 M LiPF6 ethylene carbonate/dimethyl carbonate (EC:DMC) and in 1-buthyl-1-methyl pyrrolidinium is (trifluoromethyl) sulfonylimide ([BMP][TFSI]) containing 1 M Li[TFSI]. The potential window of [BMP][TFSI] measured on Ti current collector remains not considerably influenced by addition of Li[TFSI]. The type of electrolyte does not influence the voltammetric behavior of the amorphous TiO2 nanotube layers, whereas in case of anatase there is a definite inhibition of the Li intercalation in 1 M Li[TFSI] [BMP][TFSI], expressed by increasing the peak-to-peak voltage difference between the Li insertion and de-insertion processes. The observed phenomenon is discussed in terms of viscosity difference between both electrolytes. ___________________________________________________________________________ page 76 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS TiO2 nanotube structures displayed a stable galvanostatic cycling, reaching the theoretical capacity of TiO2 structure and high current efficiencies in both Li ion containing media. QSPR study on the viscosity of bis(trifluoromethylsulfonyl)imide-based ionic liquids Journal of Molecular Liquids, 184, 2013, 51-59 Guangren Yu, Lu Wen, Dachuan Zhao, Charles Asumana, Xiaochun Chen Viscosity is a vital physical property of ionic liquids (ILs). In this work, quantitative structure–property relationship (QSPR) studies are performed for the viscosity of bis(trifluoromethylsulfonyl)imide-based ILs. Eight QSPR correlation equations are obtained for viscosities at 283 K, 293 K, 298 K, 303 K, 313 K, 323 K, 333 K, and 343 K, with R2 > 0.82. It is observed that the descriptors are mainly composed of quantum chemical, electrostatic, and constitutional species. Unlike molecular-type solvents, the interionic electrostatic interaction, accompanied by H-bonding interaction, has the most important effect on viscosity of ionic liquids; furthermore, the importance of different interionic interactions for the viscosity tends to change with temperature. To rationally design and synthesize the ILs with desired viscosity, the ionic structure and cation–anion interaction should be carefully tailored. Applicability of ionic liquid electrolytes to LaSi2/Si composite thick-film anodes in Li-ion battery Journal of Power Sources, 235, 2013, 29-35 Hiroyuki Usui, Masahiro Shimizu, Hiroki Sakaguchi Anode performances of LaSi2/Si composite thick-films were investigated in ionic liquids as Li-ion battery electrolytes containing cations of N-methyl-Npropylpiperidinium (PP13) or 1-ethyl-3-methylimidazolium and anions of bis(fluorosulfonyl)amide (FSA) or bis(trifluoromethanesulfonyl) amide. The LaSi2/Si electrode exhibited much better performance in PP13-FSA compared with the other electrolytes including a conventional organic solvent one: the reversible capacity at the 250th cycle and its retention were 800 mA h g−1 and 80%. The excellent performance is attributed to a higher stability of PP13 cations against a cathodic decomposition and an easier desolvation of Li ions and FSA anions at the electrode/electrolyte interface. This result offers a promising applicability of ionic liquid electrolyte to various Si-based anodes with high performances by architecture of cation and anion structures. Alkoxy substituted imidazolium-based ionic liquids as electrolytes for lithium batteries ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 77 PUBLICATIONS Journal of Power Sources, 235, 2013, 142-147 S. Ferrari, E. Quartarone, C. Tomasi, D. Ravelli, S. Protti, M. Fagnoni, P. Mustarelli The design and the optimization of new electrochemically stable and safer electrolytes for both Li-ion and Li–air/Li–O2 batteries is a key-target in the field of clean energy. Ionic liquids (ILs) were often indicated as components of the electrolytes of the future, because they could fulfil all the requirements for the use in electronic devices and they also address the safety issues for large-scale applications. In this work, two ether-functionalized ILs, namely 1-(2-methoxyethyl)-3methylimidazolium TFSI (IMI1,2O1TFSI) and 3-(2-(2-methoxyethoxy)ethyl)-1methylimidazolium TFSI (IMI1,1O2O1TFSI) were synthesized and characterised from a physical and electrochemical point of view. The thermal features, viscosity, conductivity and electrochemical stability were compared with those of an alkyl-IMITFSI (BuMeIMITFSI) in order to evaluate the influence of the alkoxy-groups on the electrolyte performances. Preliminary battery tests in Li/LiFePO4 cells containing solutions of IL-LiTFSI mixed with EC/DEC as electrolytes were also performed to address the cycling behaviour and the delivered capacity. Lithium–oxygen cells with ionic-liquid-based electrolytes and vertically aligned carbon nanotube cathodes Journal of Power Sources, 235, 2013, 251-255 Z.H. Cui, W.G. Fan, X.X. Guo Cycle performance of Li–O2 cells with N-methyl-N-propylpiperidinium bis(trifluoromethansulfony)imide (PP13TFSI)–LiClO4 electrolytes and vertically aligned carbon nanotube (VACNT) cathodes has been investigated. It is found that both the current density and the depth of discharge have great influence on the capacity utilization, voltage polarization and cycle life. Abacusball-shaped Li2O2 particles produced at discharge are identified, and their complete decomposition at charge is confirmed. Meanwhile, formation of Li carbonates around the VACNTs is detected after the first cycle. The carbonates accumulate and gradually become predominant over Li2O2 upon cycling, leading to decrease of the discharge capacity and increase of the cell resistance. These results indicate that reduction of the carbonates formed around the VACNTs is of critical importance for improving cycle performance of the cells investigated here. Monolithic quasi-solid-state dye-sensitized solar cells based on iodine-free polymer gel electrolyte Journal of Power Sources, 235, 2013, 243-250 ___________________________________________________________________________ page 78 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Yaoguang Rong, Xiong Li, Guanghui Liu, Heng Wang, Zhiliang Ku, Mi Xu, Linfeng Liu, Min Hu, Ying Yang, Meili Zhang, Tongfa Liu, Hongwei Han A monolithic quasi-solid-state dye-sensitized solar cell assembled with an iodine-free polymer gel electrolyte (IFGE) and a printable mesoscopic carbon counter electrode was developed. The IFGE was prepared by employing an ionic liquid (1,2-dimethyl-3-propylimidazolium iodide, DMPII) as the charge transfer intermediate and a polymer composite as the gelator without the addition of iodine, exhibiting high conductivity and non-absorption characters. The dependences of ionic conductivity and photovoltaic performance on DMPII concentration in the IFGE were investigated. An overall power conversion efficiency (PCE) of 4.94% could be obtained for the IFGE with an ionic conductivity of 21.18 mS cm−2 under 100 mW cm−2 AM 1.5 illumination. The effects of additives lithium iodide (LiI) and N-methylbenzimidazole (NMBI) on the photovoltaic performance of the devices were also investigated. An optimal efficiency of up to 6.97% was obtained and the results were substantiated by incident photon-to-current conversion efficiency (IPCE) spectrum, electrochemical impedance spectroscopy (EIS) and intensity modulated photovoltage spectroscopy (IMVS) measurements. Probing subsistence of ion-pair and triple-ion of an ionic salt in liquid environments by means of conductometric contrivance The Journal of Chemical Thermodynamics, 63, 2013, 52-59 Ishani Banik, Mahendra Nath Roy Qualitative and quantitative analyses of molecular interaction prevailing in ionic salt-organic solvent media, probed by electrical conductances have been reported. Tetrabutylammonium tetrafluoroborate [Bu4NBF4] in acetonitrile (CH3CN), methanol (CH3OH), dimethylsulfoxide (DMSO) and 1,3-dioxolane (1,3-DO) have been studied at 298.15 K. The extent of interaction is expressed in terms of the association constant (KA) and shows the interaction to be a function of viscosity. Limiting molar conductances (Λo), association constants (KA), and the association diameter (R) for ion-pair formation have been analyzed using the Fuoss conductance-concentration equation (1978). The observed molar conductivities were explained by the formation of ion-pairs (M++X− ↔ MX, KP) and triple-ions (2M+ + X− ↔ M2X+; M+ + 2X− ↔ MX2−, KT). The Walden product is obtained and discussed. The deviation of the conductometric curves (Λ vs ) from linearity for the electrolyte in 1,3-dioxolane indicates triple-ion formation, and therefore the corresponding conductance data have been analyzed by using the Fuoss–Kraus theory of triple-ions. The limiting ionic conductances () have been calculated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu4NBPh4] as the “reference electrolyte” method along with a numerical evaluation of ion-pair and triple-ion formation constants (KP ≈ KA and KT). The ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 79 PUBLICATIONS results have been interpreted in terms of solvent properties and configurational theory. Densities of a dissolving mixture of molten (AgI + NaCl) The Journal of Chemical Thermodynamics, 63, 2013, 84-87 V.P. Stepanov, N.P. Kulik, K.G. Peshkina The densities of a molten mixture of (0.5 AgI + 0.5 NaCl) were measured along the saturation line over a wide temperature range by the hydrostatic weight method to establish the peculiarities of the mixing of salts with different chemical bonds. We showed that the difference between the magnitudes of the densities for the coexisting phases decreases with increasing temperature and becomes equal to zero at 1063.5 K. This temperature corresponds to the critical phase transition point, Tc. The temperature dependence of the difference in densities, Δρ, is described by equation Δρ/ρc ≈ , where ρc is the density at Tc. The index β = 0.476 occurs at a lower value than that found for alkali halide melts (β = 0.52) where long-range Coulombic forces between ions prevail. Solubilities of some gases in four immidazolium-based ionic liquids The Journal of Chemical Thermodynamics, 63, 2013, 88-94 Waheed Afzal, Xiangyang Liu, John M. Prausnitz The synthetic-volumetric method is used for rapidly measuring solubilities of sparingly-soluble gases in monoethylene glycol and in four ionic liquids. Known molar quantities of solute and solvent are charged into an equilibrium vessel. Measured quantities at equilibrium include: temperature, pressure, quantities of fluids, and volumes of the gas and liquid phases in the equilibrium vessel. These measurements enable calculation of equilibrium compositions using material balances. No sampling or chemical analyses are required. Solubilities are reported for carbon dioxide, krypton, oxygen, and hydrogen in monoethylene glycol, l-n-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4], l-n-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][Tf2N], or 1-ethyl-3-methylimidazolium acetate [EMIM][AC]. Solubilities were measured over the temperature range (298 to 355) K and for pressures up to about 7 MPa using two different pieces of equipment, both based on the volumetric method: a low-pressure glass apparatus and a high-pressure stainless-steel apparatus. Special emphasis is given to experimental reliability to assure consistent data. ___________________________________________________________________________ page 80 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS P–V–T properties of binary mixtures of the ionic liquid 1-butyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide with anisole or acetophenone at elevated pressures The Journal of Chemical Thermodynamics, 63, 2013, 95-101 Elisabeth Widowati, Ming-Jer Lee The isothermal densities of pure ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C4mim][NTf2], and its mixtures with anisole or acetophenone were measured by using a vibrating tube densimeter over temperatures ranging from (298.15 to 348.15) K and pressures from (0.1 to 50) MPa. The Tait equation was used to correlate the density data and accurately represents densities varying with pressure at given temperature and composition. The excess volumes were calculated from the experimental data and found that those are all negative, except for (acetophenone + [C4mim][NTf2]) at 298.15 K with containing acetophenone of 0.1 in mole fraction. The modified Redlich– Kister was applied to correlate the excess volumes. The Flory–Orwoll–Vrij (FOV) and the Schotte equations of state were also employed to correlate the density data over entire experimental conditions. Solubility and phase behavior of binary systems containing salts based on transitional metals The Journal of Chemical Thermodynamics, 63, 2013, 123-127 Małgorzata E. Zakrzewska, Ana B. Paninho, Marta F. Môlho, Ana V.M. Nunes, Carlos A.M. Afonso, Andreia A. Rosatella, Joana M. Lopes, Vesna NajdanovicVisak Tri(1-ethyl-3-methylimidazolium) gadolinium hexachloride ([emim]3[GdCl6]), tri(1-butyl-3-methylimidazolium) hexagadolinium chloride ([bmim]3[GdCl6]), di(tetramethylammonium) manganese tetrachloride ([TMA]2[MnCl4]) and cholinium tetrachloroferrate ([Chol][FeCl4]) were synthetized and their solubility in water, ethanol, 1-propanol and 1-butanol were determined as a function of temperature. Activity coefficients were calculated and their comparison with ideal solutions is discussed. The experimental data were correlated successfully by means of the semi-empirical Grant equation. In addition, melting point depression effect of high pressure carbon dioxide was studied. Phase equilibria study of the (N-octylisoquinolinium thiocyanate ionic liquid + aliphatic and aromatic hydrocarbon, or thiophene) binary systems The Journal of Chemical Thermodynamics, 63, 2013, 128-134 Marta Królikowska, Monika Karpińska Binary liquid + liquid phase equilibria for 8 systems containing Noctylisoquinolinium thiocyanate, [C8iQuin][SCN] and aliphatic hydrocarbon (n___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 81 PUBLICATIONS hexane, n-heptane), cyclohexane, aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene) and thiophene have been determined using dynamic method. The experiment was carried out from room temperature to the boiling-point of the solvent at atmospheric pressure. For the tested binary systems the mutual immiscibility with an upper critical solution temperature (UCST) for {IL + aliphatic hydrocarbon, or thiophene} were observed. The immiscibility gap with lower critical solution temperature (LCST) for the {IL + aromatic hydrocarbon} were determined. The parameters of the LLE correlation equation for the tested binary systems have been derived using NRTL equation. The phase equilibria diagrams presented in this paper are compared with literature data for the corresponding ionic liquids with Nalkylisoquinolinium, or N-alkylquinolinium cation and with thiocyanate – based ionic liquids. The influence of the ionic liquid structure on mutual solubility with aliphatic and aromatic hydrocarbons and thiophene is discussed. Electrodeposition of Cu–In alloys from a choline chloride based deep eutectic solvent for photovoltaic applications Electrochimica Acta, 103, 2013, 15-22 João C. Malaquias, Marc Steichen, Matthieu Thomassey, Phillip J. Dale Electrodeposition and post-annealing is a promising low-cost approach to the growth of Cu(In,Ga)Se2 for photovoltaic applications. However, In and Ga electrodeposition is not facile from aqueous electrolytes. Efficient electrodeposition can be achieved by using deep eutectic solvent (DES) based electrolytes since solvent decomposition reactions (such as hydrogen evolution reaction in water) do not occur. In this work, the electrochemical behavior of InCl3 and CuCl2–InCl3 on the DES 1:2 choline chloride:urea (ChCl:U) on a Mo rotating disk electrode is studied via cyclic voltammetry. The deposited Cu–In thin films are characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) in terms of morphology and composition and X-ray diffraction (XRD) regarding crystal structure. The cyclic voltammetric studies on the ChCl:U– CuCl2–InCl3 system showed multiple cathodic and anodic responses, which were assigned to various crystalline phases. The crystalline phases, composition and morphology of the deposits were potential dependent. Cu–In intermetallics formation is studied as a function of deposition potential and electrolyte composition. Cu–In metal precursors were thermally annealed under selenium pressure to form CuInSe2. An electrochemical study of benzofuran derivative in modified electrodebased CNT/ionic liquids for determining nanomolar concentrations of hydrazine Electrochimica Acta, 103, 2013, 77-84 ___________________________________________________________________________ page 82 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Mohammad Mazloum-Ardakani, Alireza Khoshroo The electrochemical oxidation of 7-(1,3-dithiolan-2-yl)-9, 10-dihydroxy-6Hbenzofuro [3,2-c] chromen-6-on (as a benzofuran derivative) in carbon nanotube paste electrode-based ionic liquids was studied the in aqueous solution. A carbon paste electrode (CPE) modified with benzofuran derivative (DBC) and takes the advantages of ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate and carbon nanotube (CNTs) was constructed and used as an excellent sensor electrocatalyst to oxidation of hydrazine. This new electrode due to its enhanced conductivity presented very large current response from electroactive substrates. The modified electrode was characterized by a scanning electron microscope, electrochemical impedance spectroscopy (EIS) and voltammetry. Electrochemical behavior of hydrazine at the modified electrode had been investigated in pH 7.0 phosphate buffer solution by cyclic voltammetry, chronoamperometry and differential pulse voltammetry (DPV). The results showed an efficient catalytic activity of the electrode for the electrooxidation of hydrazine, which leads to a reduction in its overpotential by more than 480 mV. Differential pulse voltammetry (DPV) of hydrazine at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 66 nM. DPV was used for quantitation of hydrazine in water samples by the standard addition method. A reliable determination method of stability limits for electrochemical double layer capacitors Electrochimica Acta, 103, 2013, 119-124 D. Weingarth, H. Noh, A. Foelske-Schmitz, A. Wokaun, R. Kötz A reliable method for the determination of regions of electrochemical stability of electrolytes for electrochemical double layer capacitors (EDLC) by means of potential window opening measurements is presented. For this purpose, a new evaluation method for the anodic and cathodic potential limits of electrochemical systems utilizing high surface area carbon electrodes is suggested. A change of 5% in the faradaic current contribution within a potential step of 1 V to the overall current is proposed as new stability criterion. The results of seven ionic liquids (IL) and three standard electrolytes dissolved in acetonitrile (AN) or propylene carbonate (PC) at RT are presented. For two electrolytes a temperature dependent study is conducted. The feasibility of the new criterion is verified by full cell constant voltage aging experiments. The IL [EMIM][BF4] displays a maximum cell voltage of 3.5 V at RT, which is, compared to standard electrolytes, an increase of about 0.5 V. Effect of SiO2 on conductivity and structural properties of PEO–EMIHSO4 polymer electrolyte and enabled solid electrochemical capacitors ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 83 PUBLICATIONS Electrochimica Acta, 103, 2013, 174-178 Sanaz Ketabi, Keryn Lian The effect of an amorphous SiO2 nano-filler on ionic conductivity and crystallinity of poly(ethylene oxide) (PEO)–1-ethyl-3-methylimidazolium hydrogensulfate (EMIHSO4) electrolyte has been investigated. After addition of the filler, the ionic conductivity of the electrolyte reached 2.15 mS/cm at room temperature, a more than 2-fold increase over the electrolyte without filler. Structural and thermal analyses indicated that incorporation of SiO2 into PEO– EMIHSO4 improved and retained the amorphous phase by impeding PEO crystallization. The SiO2 filler was also found to be effective in facilitating ionic conduction via promoting the dissociation of EMIHSO4. Solid electrochemical double layer capacitor (EDLC) devices, leveraging the PEO–EMIHSO4 electrolyte with SiO2 filler, showed a fast capacitive response at 1 V/s and stable cycle life. Electrodeposition and corrosion characterisation of micro- and nanocrystalline aluminium from AlCl3/1-ethyl-3-methylimidazolium chloride ionic liquid Electrochimica Acta, 103, 2013, 211-218 Ashraf Bakkar, Volkmar Neubert This study reports on the electrodeposition of Al from AlCl3/1-ethyl-3methylimidazolium chloride (EMIC) ionic liquid, with the aim at determination of the mechanism applied and correlation of deposition kinetics and coulombic current efficiency with the microstructure and corrosion behaviour of Al deposits. Cyclic voltammetry studies were conducted on both platinum and steel substrates with various scanning rates and reversal potentials. Potentiostatic electrodeposition experiments were applied to obtain functional Al layers on low carbon steel substrates and the effect of deposition potential on the deposit morphology and crystal size was investigated using SEM-EDX and XRD. Nanocrystalline Al deposits were obtained on low carbon steel substrates using polarisation potentials more negative to −600 mVvs Al, and the Al crystallite size was scaled down to 28 nm at −700 mVvs Al. Nano-crystalline deposits, with brighter and flatter surfaces, showed higher corrosion resistance in aqueous chloride solutions. Subsequent redox transitions as a tool to understand solvation in ionic liquids Electrochimica Acta, 103, 2013, 243-251 Viktoriya A. Nikitina, Franziska Gruber, Martin Jansen, Galina A. Tsirlina ___________________________________________________________________________ page 84 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ionic liquid (IL) solvent effect on the redox potential values of three anionic reactants (one quinone derivative and two polytungstates) is investigated by means of cyclic voltammetry. Redox potential dependencies on the solvent nature are analyzed in two series of ILs (comprising the same cation and the same anion), and compared with literature data for molecular solvents. Very positive redox potential values for selected reactants in ILs can be explained assuming strong association between anionic forms of reactants and cations of IL, which was found to be more pronounced than that in tetraalkylammonium electrolyte solutions in low- and moderate-permittivity molecular solvents. It is shown that ion–ion interactions are primarily responsible for solvation energetics in ILs, and the reduction of multicharged anions is accompanied by association of the product with cation. The importance of the account for ionic association when considering kinetics and equilibria in ILs is stressed. Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors Electrochimica Acta, 102, 2013, 120-126 Aurélien Boisset, Johan Jacquemin, Mérièm Anouti Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from −60 °C to 280 °C, low vapor pressure, and high ionic conductivity up to 28.4 mS cm−1 at 150 °C and at xLiTFSI = 1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius’ Law and Vogel–Tamman–Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO4) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO4) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 85 PUBLICATIONS Template-free electrosynthesis of crystalline germanium nanowires from solid germanium oxide in molten CaCl2–NaCl Electrochimica Acta, 102, 2013, 369-374 Huayi Yin, Wei Xiao, Xuhui Mao, Weifeng Wei, Hua Zhu, Dihua Wang Germanium nano-materials are attractive due to their potential application prospects in electronic, information and energy industry. Herein we report a one-step preparation of crystalline germanium nanowires (Ge-NWs) by direct electrochemical reduction of solid GeO2 in molten CaCl2–NaCl at 600 °C with a current efficiency of ~86% and an energy consumptions as low as 3.26 kW h (kg Ge)−1. The cyclic voltammogram of the GeO2-filled cavity electrode shows that the onset electroreduction potential of GeO2 is −1.0 V vs. Ag/Ag+, much more positive than the reduction potential of cations in the melt. The as-prepared Ge-NWs are of high aspect ratio, high purity and good crystallinity according to the XRD, EDX, SEM and TEM characterizations. The present approach provides a simple and short process for the production of Ge-NWs from a costaffordable germanium precursor (GeO2). The potential applications of the obtained Ge for photodetector and infrared optical window have been also investigated by Raman and FT-IR measurements. Graphene nanosheet supported bifunctional catalyst for high cycle life Liair batteries Journal of Power Sources, 234, 2013, 8-15 Lixin Wang, Mahbuba Ara, Kapila Wadumesthrige, Steven Salley, K.Y. Simon Ng Rechargeable lithium-air batteries offer great promise for transportation and stationary applications due to their high specific energy and energy density. Although their theoretical discharge capacity is extremely high, the practical capacity is much lower and is always cathode limited. A key for rechargeable systems is the development of an air electrode with a bifunctional catalyst on an electrochemically stable carbon matrix. The use of graphene as a catalyst matrix for the air cathode has been studied in this work. A Li-air cell using an air cathode consisting of nano-Pt on graphene nanosheets (GNS) has shown promising performance at 80% energy efficiency with an average capacity of 1200 mAh g−1 and more than 20 cycles without significant loss of total energy efficiency. Replacement of Pt with a bifunctional catalyst resulted in more than 100 cycles with an average capacity of 1200 mAh g−1 and total energy efficiency of about 70%. Electrochemical impedance spectroscopy data revealed increasing solution and charge transfer resistance during cycling, which hindered the cycle life. The increased solution resistance can be attributed to the evaporation and decomposition of electrolyte especially at high charge voltages. Further investigation on ionic liquid based electrolytes in Li-air systems is being conducted. ___________________________________________________________________________ page 86 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ionic liquid electrolytes for lithium batteries: Synthesis, electrochemical, and cytotoxicity studies Journal of Power Sources, 234, 2013, 277-284 Ninu Madria, T.A. Arunkumar, Nanditha G. Nair, Avinash Vadapalli, YueWern Huang, Simon C. Jones, V. Prakash Reddy We have synthesized and determined the electrochemical and thermal stabilities of a series of 1-methyl-3-alkoxyalkyl and 1-methyl-3-fluoroalkyl imidazolium and the corresponding pyrrolidinium-based ionic liquids and estimated the cytotoxicities of representative ionic liquids. The pyrrolidinium-TFSI based ionic liquids have wide electrochemical stability (>5.7–6.2 V vs. Li/Li+) but show limited thermal stabilities and lithium cell discharge characteristics, as compared to those that are imidazolium-based (4.8–5.1 V vs. Li/Li+). The fluoroalkylderived ionic liquids typically have superior thermal stability (Td > 350 °C) as compared to the alkoxyalkyl-substituted analogues. In all these cases, TFSI− anion-based ionic liquids are thermally and electrochemically more stable than the BF4− anion-based analogues. We have also shown that the imidazoliumbased ionic liquids are relatively nontoxic and their EC50 values are comparable to their corresponding lithium salts. Reducing Li-ion safety hazards through use of non-flammable solvents and recent work at Sandia National Laboratories Review Article Electrochimica Acta, 101, 2013, 3-10 Ganesan Nagasubramanian, Kyle Fenton This article will briefly discuss the genesis of the Li-ion chemistry and its meteoric rise to prominence, supplanting aqueous rechargeable batteries such as NiCd and NiMH. The principal intent of this article is to discuss the issues with thermal instability of common Li-ion electrolytes, which detract from the positive attributes of this chemistry. The development of an innovative low-cost non-flammable electrolyte will greatly improve the safety and reliability of lithium batteries, a key technological hurdle that must be overcome for the wider application of this chemistry. This article will also include the advancements made in combating/mitigating solvent flammability through the addition of fire retardants, fluoro-solvents, ionic liquids etc. The scope of the article will be limited to the flammability of non-aqueous solvents and will not include the thermal instability issues of anodes and cathodes. We will elaborate using examples from our in-house research aimed at mitigating solvent flammability by using hydrofluoro ethers (HFEs) as a cosolvent. Additionally, we will describe in-house capabilities for prototyping 18,650 cells and in-house thermal abuse test capabilities that allow us to evaluate materials and their thermal responses in actual cell configurations ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 87 PUBLICATIONS LiNi0.5Mn1.5O4 spinel cathode using room temperature ionic liquid as electrolyte Electrochimica Acta, 101, 2013, 151-157 Xuan-Wen Gao, Chuan-Qi Feng, Shu-Lei Chou, Jia-Zhao Wang, Jia-Zeng Sun, Maria Forsyth, Douglas R. MacFarlane, Hua-Kun Liu In this study, LiNi0.5Mn1.5O4 (LNMO) nanoparticles were prepared as a 5 V cathode material via a rheological phase method and annealed at different temperatures: 680 °C, 750 °C, and 820 °C. The sample annealed at 750 °C shows the best performance. A room temperature ionic liquid (RTIL) containing 1 M lithium bis(trifluoromethanesulfonyl) imide (LiNTf2) in N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (C4mpyrNTf2) was used as novel electrolyte in conjunction with the LNMO cathodes and their electrochemical properties have been investigated. The results show that the LNMO using RTIL as electrolyte has better coulombic efficiency and comparable discharge capacities to those of the cells assembled with standard liquid electrolyte (1 M LiPF6 in ethylene carbonate/diethyl carbonate). Electrochemical impedance spectroscopy shows that the RTIL is much more stable as the electrolyte for LiNi0.5Mn1.5O4 than the conventional electrolyte. Oxygen reduction voltammetry on platinum macrodisk and screen-printed electrodes in ionic liquids: Reaction of the electrogenerated superoxide species with compounds used in the paste of Pt screen-printed electrodes? Electrochimica Acta, 101, 2013, 158-168 Junqiao Lee, Krishnan Murugappan, Damien W.M. Arrigan, Debbie S. Silvester Screen-printed electrodes (SPEs) are widely investigated as simple, threeelectrode planar surfaces for electrochemical sensing applications, and may be ideal for gas sensing purposes when combined with non-volatile room temperature ionic liquids (RTILs). In this report the suitability of SPEs with RTIL solvents has been investigated for oxygen detection. Oxygen reduction has been studied on commercially available platinum SPEs in eight RTILs. Cyclic voltammetric wave shapes were found to be significantly different on Pt SPE surfaces compared to conventional solid Pt macroelectrodes, suggesting a possible reaction of the electrogenerated superoxide with the compounds that make up the ink/paste of the SPE surface. The only RTIL that did not show such drastically different voltammetry was one that contained a pyrrolidinium cation, suggesting a more chemically stable solvent environment compared to the other imidazolium and phosphonium cations studied. The analytical utility was then studied on four SPE surfaces (carbon, gold, platinum and silver) in two RTILs (one with a pyrrolidinium and one with an imidazolium cation) and linear responses were observed between current and % concentration in the range 10– 100% O2. This suggests that SPEs may indeed be suitable for oxygen sensing in some RTILs, but significantly more pre-treatment of the surface is required to ___________________________________________________________________________ page 88 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS obtain reliable results. However, the reaction of superoxide with the SPE ink, together with a noticeable deterioration of the signal over time, suggests that this type of sensing platform may only be suitable for “single-use” oxygen sensing applications. Cobalt(II) phosphonate coordination polymers: Synthesis, characterization and application as oxygen evolution electrocatalysts in aqueous media and water-saturated hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid Electrochimica Acta, 101, 2013, 201-208 Yuping Liu, Si-Xuan Guo, Alan M. Bond, Jie Zhang, Shaowu Du Four cobalt phosphonate coordination polymers Co[(CH3PO3)(H2O)] (1), Co[(C2H5PO3)(H2O)] (2), Co[(C4H9PO3)(H2O)] (3) and Co[(C6H5PO3)(H2O)] (4) have been synthesized using a hydrothermal method. Their crystal structures have been characterized by X-ray diffraction and all exhibit two-dimensional polymer structures. The water oxidation catalytic activities of these polymers have been studied for the first time using electrochemical methods in both aqueous solutions and water-saturated [BMIM][PF6] ionic liquid (BMIM = 1butyl-3-methylimidazolium). The results reveal that these polymers are able to catalyze water oxidation in aqueous media but are not fully stable in this environment. However, they are more stable and retain significant catalytic activity towards water oxidation in water-saturated [BMIM][PF6] and addition of a buffer is not required. The catalytic activity decreases in the sequence of 1 > 2 > 3 > 4. Consequently, water-saturated [BMIM][PF6] provides a good medium for catalytic water oxidation with this type of coordination polymer. Influence of solvation on the structural and capacitive properties of electrical double layer capacitors Electrochimica Acta, 101, 2013, 262-271 Céline Merlet, Mathieu Salanne, Benjamin Rotenberg, Paul A. Madden We use molecular dynamics simulations to explore the impact of a non-ionic solvent on the structural and capacitive properties of supercapacitors based on an ionic liquid electrolyte and carbon electrodes. The study is focused on two pure ionic liquids, namely 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium tetrafluoroborate, and their 1.5 M solutions in acetonitrile. The electrolytes, represented by coarse-grained models, are enclosed between graphite electrodes. We employ a constant potential methodology which allows us to gain insight into the influence of solvation on the polarization of the electrodes as well as the structural and capacitive properties of the electrolytes at the interface. We show that the interfacial ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 89 PUBLICATIONS characteristics, different for two distinct pure ionic liquids, become very similar upon mixing with acetonitrile. Molecular dynamics simulation of diffusion of nitrobenzene in 3methylimidazolium hexafluorophosphate ionic liquids Journal of Molecular Liquids, 183, 2013, 1-7 Jian-Ping Zeng, Yun-Shan Bai, Song Chen, Chun-An Ma The diffusions of nitrobenzene (PhNO2) in the three kinds of ionic liquids (ILs), i.e. 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF6]), 1-butyl3-methylimidazolium hexafluorophosphate ([Bmim][PF6]), and 1-hexyl-3methylimidazolium hexafluorophosphate ([Hmim][PF6]) were examined by molecular dynamics (MD) simulation. Diffusion coefficients of PhNO2, imidazole (Mim) cation and PF6 anion were calculated based on the Einstein equation. The influence of the different ionic liquids on the diffusion of PhNO2 was discussed. The results showed that at the same simulation concentration, the diffusion coefficients of all the species decrease with an increase of the side chain of 3-methylimidazolium hexafluorophosphate ionic liquids in the model system. These simulation results are in good agreement with the electrochemical experiment reported by Chen et al. Analyses of the pair correlation functions (PCFs) of the simulation systems showed that the non-bond and hydrogen bond interactions are formed between PhNO2–ionic liquid systems. The Coulomb and van der Waals (vdW) interactions are helpful for the diffusion of PhNO2 in 3methylimidazolium hexafluorophosphate ionic liquids and the contribution from the vdW interaction is significantly greater than that from the Coulomb interaction in the system. From the related coefficient (R) of mean square displacement (MSD) curve and PCFs, the diffusion of PhNO2 in [Hmim][PF6] ionic liquids is weaker than the other two ionic liquids. This study has provided a theoretical direction for the experiments on the mass transfer of PhNO2 in ionic liquids. Mild basic ionic liquids as catalyst for the multi-component synthesis of 7amino-1,3-dioxo-1,2,3,5-tetrahydropyrazolo[1,2-a][1,2,4]triazole and 6,6dimethyl-2-phenyl-9-aryl-6,7-dihydro-[1,2,4]triazolo[1,2-a]indazole1,3,8(2H,5H,9H)-trione derivatives Journal of Molecular Liquids, 183, 2013, 8-13 Hamid Reza Shaterian, Kobra Azizi Synthesis of 7-amino-1,3-dioxo-1,2,3,5-tetrahydropyrazolo[1,2-a][1,2,4]triazole derivatives by a three component reaction of aryl aldehydes, 4-phenylurazole and malononitrile or ethyl cyanoacetate in the presence of catalytic amount of weak basic ionic liquids such as N-butyl-N-methylpyrrolidinium acetate, 1-butyl3-methylimidazolium imidazolide, and 1-ethyl-3-methylimidazolium acetate ___________________________________________________________________________ page 90 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS under solvent-free conditions is described. In addition, preparation of 6,6dimethyl-2-phenyl-9-aryl-6,7-dihydro-[1,2,4]triazolo[1,2-a]indazole1,3,8(2H,5H,9H)-trione derivatives from the reaction of aryl aldehydes, 4phenylurazole and dimedone in the presence of mentioned catalysts under mild, ambient and solvent-free conditions at room temperature is reported. Reusability of catalysts, and easy isolation of products along with excellent yields are the advantages of these methods. Protic [TBD][TFA] ionic liquid as a reusable and highly efficient catalyst for N-formylation of amines using formic acid under solvent-free condition Journal of Molecular Liquids, 183, 2013, 45-49 Seyed Meysam Baghbanian, Maryam Farhang Trifluoroacetate guanidinium salt [TBD][TFA] ionic liquid was used as a recyclable and reusable catalyst for the synthesis of formamides. Primary and secondary amines were reacted with formic acid to afford N-formyl derivatives in high yield under solvent-free condition at room temperature. Sites of protonation and copper(II)-complexation in protic ionic liquids comprised of N-hexylethylenediaminium cation Journal of Molecular Liquids, 183, 2013, 50-58 Mayu Watanabe, Shinobu Takemura, Sayaka Kawakami, Emi Syouno, Hiromichi Kurosu, Masafumi Harada, Masayasu Iida Protonation sites of a chelating mono-protic ionic liquid (PIL) comprising Nhexylethylenediaminium (= HHexen+) depending on the counter anion were studied by 15N and 13C NMR spectroscopy and DFT calculation. In the case of the bis(trifluoromethanesulfonyl) amide (= TFSA−) PIL, the protonation occurred almost at the secondary amine, whereas the protonation occurred preferentially at the primary amine in the trifluoroacetate (= TFA−) PIL. The formation of a chelating copper(II) complex with the cationic unit of the PIL despite the electrostatic repulsion was revealed using the paramagnetic broadenings of the 13C NMR spectra of the PILs. Synthesis, characterization and application of magnetic room temperature dicationic ionic liquid as an efficient catalyst for the preparation of 1,2azidoalcohols Journal of Molecular Liquids, 183, 2013, 14-19 Bijan Mombani Godajdar, Ali Reza Kiasat, Mohammad Mahmoodi Hashemi An environmentally benign, aqueous synthesis of 1,2-azidoalcohols via regioselective ring opening of their epoxides using magnetic imidazolium based dicationic room temperature ionic liquid, [pbmim](FeCl4)2, as an efficient ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 91 PUBLICATIONS magnetic phase transfer catalyst in water has been described. The present approach offers the advantages of clean reaction, simple methodology, short reaction time, high yield, easy purification and reusable catalyst. N-n-Butyl-N-methylpyrrolidinium hexafluorophosphate-added electrolyte solutions and membranes for lithium-secondary batteries Journal of Power Sources, 233, 2013, 104-109 Akiko Tsurumaki, Maria Assunta Navarra, Stefania Panero, Bruno Scrosati, Hiroyuki Ohno Polymer electrolytes were prepared using 1 M LiPF6 in ethylene carbonate– dimethyl carbonate 1:1 wt/wt (LP 30 SelectiLyte™: LP 30 henceforth), N-nbutyl-N-methylpyrrolidinium hexafluorophosphate ([Py14]PF6), and poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP). To determine adequate composition of liquid electrolyte, we investigated the effect of the ratio of [Py14]PF6 to LP 30, in terms of thermal stability, ionic conductivity and electrochemical stability. The solution, LP 30 with 30 wt% [Py14]PF6, gave better properties compared to pure LP 30 and other mixtures examined in this study. Then this was used for galvanostatic charge–discharge tests of a lithium cell. The cell, with the chosen electrolyte solution, demonstrated reversible capacity reaching the theoretical values, when Li metal was combined with LiFePO4 or Li4Ti5O12 electrode. A polymer membrane was prepared by combining the chosen solution with PVdF-HFP matrix. The ionic conductivity of this membrane was 4 × 10−4 S cm−1 at room temperature. Furthermore, the polymer electrolyte displayed reasonable thermal stability, reflecting the properties of [Py14]PF6 in improving the performance of the polymer electrolyte. High voltage and safe electrolytes based on ionic liquid and sulfone for lithium-ion batteries Journal of Power Sources, 233, 2013, 115-120 Jin Xiang, Feng Wu, Renjie Chen, Li Li, Huigen Yu Novel binary electrolytes based on ionic liquid (N-butyl-methyl piperidinium bis(trifluoro-methylsulfonyl)imide, PP14-TFSI) and sulfone (tetramethylene sulfone, TMS) have been prepared and examined for use in lithium-ion batteries. The addition of sulfone is expected to improve the lithium salts solvability, ionic conductivity and electrode compatibility of the ionic liquid greatly. More importantly, the addition of sulfone is not expected to deteriorate the peculiar properties of the ionic liquid, such as the wide electrochemical window and nonflammability. Experimental results have shown that the reversible discharge capacities of the Li/LiFePO4 half-cell, which contains a 0.5 M LiTFSI/(60%) PP14-TFSI/(40%) TMS mixed electrolyte at a current density of 0.05 C and 1 C, can reach up to 160 and 150 mAh g−1, respectively, which are much higher than the discharge capacity achieved using the pure ionic liquid electrolyte under the same conditions. Furthermore, lithium difluoro(oxalato)borate (LiDFOB) has ___________________________________________________________________________ page 92 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS been found to have positive effects on the battery performance of the mixed electrolytes. The 0.5 M LiDFOB/(60%) PP14-TFSI/(40%) TMS mixed electrolyte exhibits better compatibility with the Li1.2Ni0.2Mn0.6O2 cathode than conventional electrolytes, where an initial discharge capacity of 255 mAh g−1 is obtained and a stable capacity of above 230 mAh g−1 is retained after 30 cycles. Measurements of activity coefficients at infinite dilution for organic solutes and water in N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] using GLC The Journal of Chemical Thermodynamics, 62, 2013, 1-7 Marta Królikowska, Monika Karpińska, Marek Królikowski This work is a continuation of our research of ionic liquids (ILs) to investigate the possibility of using them as a solvent for the separation processes, especially for extraction of aromatic from aliphatic hydrocarbons. New data of the activity coefficients at infinite dilution, were determined for 53 solutes including: nalkanes, alk-1-enes, alk-1-ynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, acetonitrile, pyridine, 1-nitropropane and water in the ionic liquid: N-hexylisoquinolinium thiocyanate, [HiQuin][SCN] using inverse gas chromatography at wide range of temperature from (308.15 to 368.15) K. From the temperature dependence of the basic thermodynamic function, that is partial molar excess Gibbs free energies, , enthalpies and entropies Tref at infinite dilution were calculated at a wide temperature range. Additionally the gas–liquid partition coefficients, KL were determined. The selectivities for nheptane/toluene, cyclohexane/benzene, n-heptane/xylenes separation problems were calculated directly from the experimental values of and compared to the studies from the recent literature for other ionic liquids. Equilibrium partitioning of drug molecules between aqueous and amino acid ester-based ionic liquids The Journal of Chemical Thermodynamics, 62, 2013, 27-34 Jun Jing, Zhiyong Li, Yuanchao Pei, Huiyong Wang, Jianji Wang In this work, a series of novel room temperature ionic liquids (ILs) have been synthesized with cheap, naturally α-amino acid ester as cations and bis(trifluoromethylsulfonyl)imide as anion. The glass transition temperature and thermal decomposition temperature of these ILs, partition coefficients of some coumarins and purine alkaloids between water and the amino acid ester-based ILs at T = 298.15 K, and Gibbs energy, enthalpy and entropy changes for the transfer of caffeine and 6,7-dihydroxycoumarin from water to [LeuC2][Tf2N] have been determined. It is shown that these ILs are highly effective materials for the extraction of drug compounds like coumarin, 4-hydroxycoumarin, 7hydroxycoumarin, 3-aminocoumarin, coumarin-3-carboxylic acid, 6,7dihydroxycoumarin, 6,7-dihydroxy-4-methylcoumarin, caffeine, theobromine, theophylline, inosine, and 2,6-diaminopurine. The partition process is driven by ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 93 PUBLICATIONS enthalpy term, and partition coefficients of the drug molecules increase with the increase of hydrophobicity of both the drug molecules and the ILs. Furthermore, the possible partition mechanism has been investigated from 13C NMR measurements. Interface adsorption and micelle formation of ionic liquid 1-hexyl-3methylimidazolium chloride in the toluene + water system The Journal of Chemical Thermodynamics, 62, 2013, 92-97 Simin Asadabadi, Javad Saien, Vahid Khakizadeh The influence of synthesized ionic liquid 1-hexyl-3-methylimidazolium chloride adsorption on equilibrium interfacial tension of toluene–water was studied within concentration range of (1.00 ⋅ 10−4 to 6.00 ⋅ 10−1) mol · dm−3 and temperature range of (293.2 to 313.2) K. Very similar to conventional surfactants, the interfacial tension was decreased with both of these parameters. Meanwhile, the CMC values showed a minimum value within the temperature range studied. The Frumkin adsorption isotherm that accounts for the non-ideal adsorption at the interface showed adequately well for modeling the experimental results. Accordingly quantities like interface excess concentration, adsorption tendency and interaction parameter between adsorbed molecules were obtained at different temperatures. Entropy and energy changes associated with adsorption were also obtained from the temperature dependency of interfacial tension. The adsorption tendency and efficiency increased with temperature, and the maximum interface excess concentration and electrostatic repulsion were achieved at about T = 303.2 K. Study of thermodynamic and transport properties of phosphonium-based ionic liquids The Journal of Chemical Thermodynamics, 62, 2013, 98-103 Francisco J. Deive, Miguel A. Rivas, Ana Rodríguez In this work, the experimental values of density, speed of sound, refractive index and dynamic viscosity have been obtained from T = (293.15 to 343.15) K for the three phosphonium-based ionic liquids: tributyl methyl phoshponium methylsulfate (P4441 C1SO4), tributyl ethyl phosphonium diethylphosphate (P4442 (C2)2PO4) and tributyl octyl phosphonium chloride (P4448 Cl). The isentropic compressibility has been calculated by means of the Laplace equation from the experimental speed of sound results for the three ionic liquids at different temperatures. Density, speed of sound, refractive index and isentropic compressibility have been correlated by polynomial equations. The Lorentz– Lorenz, Dale–Gladstone, Eykman, Oster, Arago–Biot, Newton and modified Eykman equations were the empirical models used to correlate satisfactorily the relationship between the densities and refractive indices of the ionic liquids selected. The temperature dependence of the experimental dynamic viscosities for the ionic liquids selected can be described by an Arrhenius-like law and by ___________________________________________________________________________ page 94 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS VFT equations. The Riedel, Narsimham, Bradford–Thodos, Yen–Woods, Rackett, Spencer–Danner, Gunn–Yamada, Hankinson–Thomson (COSTALD model), VSY, VSD, MH and LGM equations were employed to predict the densities of the pure ionic liquids. Thermodynamic surface properties of [BMIm][NTf2] or [EMIm][NTf2] binary mixtures with tetrahydrofuran, acetonitrile or dimethylsulfoxide The Journal of Chemical Thermodynamics, 62, 2013, 104-110 Monika Geppert-Rybczyńska, Jochen K. Lehmann, Javid Safarov, Andreas Heintz The surface tension, σ, of binary mixtures of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIm][NTf2] with tetrahydrofuran (oxolane, thf), acetonitrile, dimethylsulfoxide ((methylsufinyl)methane, dmso) and of 1ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMIm][NTf2] with dimethylsufoxide was measured between (293.15 and 313.15) K using the pendant drop method. On the basis of experimental σ values and activity coefficients of solutes in their solutions with ionic liquid obtained from vapor pressure measurement, Gibbs excess surface concentrations of thf, acetonitrile or dmso in mixtures with [BMIm][NTf2] or [EMIm][NTf2] were determined. The results are discussed in terms of possible interactions between ILs and aprotic polar substances. Density, refraction index and vapor–liquid equilibria of N-methyl-2hydroxyethylammonium butyrate plus (methyl acetate or ethyl acetate or propyl acetate) at several temperatures The Journal of Chemical Thermodynamics, 62, 2013, 130-141 V.H. Alvarez, S. Mattedi, M. Aznar This paper reports the densities, refraction indices, and vapor liquid equilibria for binary systems ester + N-methyl-2-hydroxyethylammonium butyrate (m-2HEAB): methyl acetate (1) + m-2-HEAB (2), ethyl acetate (1) + m-2-HEAB and propyl acetate (1) + m-2-HEAB (2). The excess molar volumes, deviations in the refraction index, apparent molar volumes, and thermal expansion coefficients for the binary systems were fitted to polynomial equations. The Peng–Robinson equation of state, coupled with the Wong–Sandler mixing rule, is used to describe the experimental data. Since the predictive activity coefficient model COSMO-SAC is used in the Wong–Sandler mixing rule, the resulting thermodynamic model is a completely predictive one. The prediction results for the density and for the vapor–liquid equilibria have a deviation lower than 1.0% and 1.1%, respectively. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 95 PUBLICATIONS Quaternary (liquid + liquid) equilibria for systems of imidazolium based ionic liquid + thiophene + pyridine + cyclohexane at 298.15 K: Experiments and quantum chemical predictions The Journal of Chemical Thermodynamics, 62, 2013, 142-150 Mitesh R. Shah, Ramalingam Anantharaj, Tamal Banerjee, Ganapati D. Yadav 1-Ethyl 3-methylimidazolium acetate [EMIM][OAc], 1-ethyl 3methylimidazolium ethylsulfate [EMIM][EtSO4] and 1-ethyl 3methylimidazolium methylsulfonate [EMIM][MeSO3] are found to be effective for the selective of a five member ring sulfur compound, viz. thiophene, and a six member ring nitrogen compound, viz. pyridine from a hydrocarbon, viz. cyclohexane at room temperature and atmospheric pressure. The liquid liquid equilibrium (LLE) data for the quaternary mixtures of ionic liquid (1) + thiophene (2) + pyridine (3) + cyclohexane (4) are experimentally determined. The experimental tie line data are successfully correlated with the Non Random Two Liquid (NRTL) and UNIversal QUAasi-Chemical (UNIQUAC) models, which provide a good correlation of the experimental data with root mean square deviation (RMSD) values less than unity for all the studied systems. The results suggest that the structure and size of the anion greatly affects the extractive performance of ionic liquids. The reliability of experimental data is ascertained by applying the quantum chemical based COnductor like Screening Model-Segment Activity Coefficient (COSMO-SAC) model. The goodness of the fit is determined by calculating the RMSD values. The RMSD values obtained for [EMIM][OAc], [EMIM][EtSO4] and [EMIM][MeSO3] are 10.4%, 8.1% and 12.2%, respectively. Pressure dependence on the viscosities of 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide and two tris(pentafluoroethyl) trifluorophosphate based ionic liquids: New measurements and modelling The Journal of Chemical Thermodynamics, 62, 2013, 162-169 Félix M. Gaciño, Xavier Paredes, María J.P. Comuñas, Josefa Fernández New experimental viscosity values for three ionic liquids, 1-butyl-2,3dimethylimidazolium tris(pentafluoroethyl)trifluorophosphate, 1-(2methoxyethyl)-1-methyl-pyrrolidinium tris(pentafluoroethyl)trifluorophosphate and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, are reported in this work. The measurements were carried out using a falling-body viscometer within the temperature range from (313.15 to 363.15) K at pressures up to 150 MPa. These values were correlated as a function of temperature and pressure with four different equations. Moreover, we perform an analysis of the dependency of viscosity on pressure and temperature based on the density scaling concept for these fluids and other three ionic liquids recently studied with the same device. ___________________________________________________________________________ page 96 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Predicting the melting points of ionic liquids by the Quantitative Structure Property Relationship method using a topological index The Journal of Chemical Thermodynamics, 62, 2013, 196-200 Fangyou Yan, Shuqian Xia, Qiang Wang, Zhen Yang, Peisheng Ma A Quantitative Structure Property Relationship (QSPR) model was developed to predict the melting points of ionic liquids (ILs) with diverse classes of cations and anions. The QSPR model was based on the general topological index (TI) proposed in our previous work. The TI was successfully used for the prediction of the decomposition temperature of ILs and the toxicity of ILs in acetylcholine esterase and Leukemia Rat Cell Line. ILs are a class of molten salts which are composed entirely of cations and anions, therefore the descriptors for ILs are generally calculated from cations and anions separately and the interaction between them is neglected. In this study, besides the two sets of TIs generated from cations and anions, a third TI was used to depict the interaction of anions and cations. The QSPR model is on the base of eight kinds of ILs, which are imidazolium, benzimidazolium, pyridinium, pyrrolidinium, ammonium, sulfonium, triazolium and guanidinium. The regression coefficient (R2) and the overall average absolute deviation (AAD) are 0.778 and 7.20%, respectively. The development of an all copper hybrid redox flow battery using deep eutectic solvents Electrochimica Acta, 100, 2013, 18-23 David Lloyd, Tuomas Vainikka, Kyösti Kontturi The performance of a redox flow battery based on chlorocuprates dissolved in an ionic liquid analogue is reported at 50 °C. The kinetics of the positive electrode reaction at a graphite electrode are favourable with a heterogeneous rate constant, k0, of 9.5 × 10−4 cm s−1. Coulombic efficiency was typically 94% and independent of current density. The small cell potential of 0.75 V and slow mass transport result in energy efficiencies of only 52% and 62% at current densities of 10 and 7.5 mA/cm2 respectively. The successful development of a separator by jellifying the electrolyte using polyvinyl alcohol is reported. Ultrafast characterization of the electron injection from CdSe quantum dots and dye N719 co-sensitizers into TiO2 using sulfide based ionic liquid for enhanced long term stability Electrochimica Acta, 100, 2013, 35-43 Victoria González-Pedro, Qing Shen, Vasko Jovanovski, Sixto Giménez, Ramon Tena-Zaera, Taro Toyoda, Iván Mora-Seró Combination of inorganic quantum dots (QDs) and organic/metallorganic dyes as supracollectors nanocomposites could have an important role on the development of efficient photovoltaic devices based on the synergistic action of the hybrid-sensitizers. Here we have analyzed the combination of CdSe QDs and ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 97 PUBLICATIONS polypyridil N719 ruthenium dye. By ultrafast transient grating measurements we show that the cascading structure (type II) of this system takes full advantage to augment electron injection and hole regeneration efficiencies. Co-sensitized TiO2 electrodes lead to an improvement in charge separation, increasing the number of injected electrons from the CdSe QDs to the TiO2 as a consequence of the suppression of back reaction, by fast regeneration of holes by the dye action. The potentiality of this supracollector system has been verified in a complete cell configuration. Sulfide/polysulfide based ionic liquid in which both sensitizers (QD and dye) are stable has been employed as hole conducting media. In spite of the limited efficiencies of the analyzed cells, the higher photocurrents measured for CdSe/N719 co-sensitization compared to the cells sensitized using a single sensitizer constitutes a valid proof of the concept. Impedance spectroscopy unveiled the recombination limitation of the analyzed cells. On the other hand, ionic liquid exhibits an enhanced cell stability maintaining cell efficiency after one week and keeping it at 80% after 21 days. The reported results highlight a huge potential of the synergetic combination of QD and dyes for improving solar cell performance and of novel sulfide/polysulfide ionic liquid-based electrolytes for enhancing long term stability and sustainability of QD sensitizers. Electrochemical quartz crystal microbalance study of Si electrodeposition in ionic liquid Electrochimica Acta, 100, 2013, 236-241 J. Komadina, T. Akiyoshi, Y. Ishibashi, Y. Fukunaka, T. Homma The electrodeposition of silicon from silicon tetrachloride in the hydrophobic room temperature ionic liquid trimethyl-n-hexyl ammonium bis(trifluoromethylsulfonyl) imide was investigated by cyclic voltammetry and chronoamperometry. In situ electrochemical quartz crystal microbalance (EQCM) impedance spectroscopy was used to estimate the mass of films during deposition. The charge efficiency estimated from EQCM measurements is ∼190–250% for four-electron silicon reduction. However, compositional analysis by XPS shows that the EQCM current efficiency estimates are artificially high due to ionic liquid inclusion in the films. Taking the mass concentration of impurities into account, the best-case estimate of current efficiency is found to be approximately 130% for constant potential deposition, suggesting silicon may not have been completely reduced at the potentials investigated, or a chemical reaction step occurs. We also consider that the EQCM analysis may include too many deviations from assumptions for accurate estimation of mass with the conditions studied. Production of Nb–Ti–Ni alloy in molten CaCl2 Electrochimica Acta, 100, 2013, 257-260 Ryunosuke Enmei, Tatsuya Kikuchi, Ryosuke O. Suzuki ___________________________________________________________________________ page 98 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A Nb–Ti–Ni hydrogen permeable alloy was synthesized as a powder using the OS process, which involves the simultaneous reduction of a mixture of Nb, Ti, and Ni oxides by Ca that is generated from molten CaCl2 via electrolysis. The mechanism confirmed that a BCC-(Nb, Ti) phase easily formed at an early stage of the reaction followed by the generation of a B2-TiNi phase from the lower oxides such as NbO and Ti2O. The oxygen content of the synthesized alloy decreased significantly to 0.27 mass% with increased electric charge. The three elements were uniformly distributed at the macroscopic level. Electrorefining reaction of sodium in sodiumbis(trifluoremethylsulfonyl)imide and tetraethylammoniumbis(trifluoremethylsulfonyl)imide mixture ionic liquid Electrochimica Acta, 100, 2013, 265-268 Mikito Ueda, Kazuya Honda, Toshiaki Ohtsuka To develop a electrorefining process of sodium for the recycling of used sodium–sulfur secondary battery, a non-aqueous electrolytic melt was investigated as a candidate for the process. A mixed ionic liquid of NaTFSI (sodium-bis(trifluoremethylsulfonyl)imide)–TEATFSI (tetraethylammoniumbis(trifluoremethylsulfonyl)imide) was selected for the electrolyte, since it has a wide potential window and a weak reactivity with metallic sodium. From AC impedance measurements, the maximum electric conductivity of 36 mS cm−1 was found for a concentration of 20 mol% NaTFSI–TEATFSI at 433 K. The cathodic deposition of liquid sodium, 99.99% pure, was obtained on a glassy carbon electrode by constant current electrolysis. The calcium concentration in the sodium was decreased from 500 to 12 ppm by the electrorefining. A cathodic current efficiency at 88% was achieved in these electrorefining experiments. Formation of niobium powder by electrolysis in molten salt Electrochimica Acta, 100, 2013, 269-274 Isamu Ueda, Masahiko Baba, Tatsuya Kikuchi, Ryosuke O. Suzuki Fine Nb2O5 powder was filled into a basket-type cathode and immersed in molten CaCl2–0.5 mol% CaO at 1173 K. Nb2O5 immediately reacted with CaO in the molten CaCl2 and formed calcium niobites that exhibited rod- or plate-like morphology. After the electrolysis of CaO with a graphite consumable anode, spherical particles of metallic niobium powder containing a residual oxygen concentration of 0.673 mass% O were obtained. Chitosan-based gel electrolyte containing an ionic liquid for highperformance nonaqueous supercapacitors Electrochimica Acta, 100, 2013, 275-280 Masaki Yamagata, Kazunari Soeda, Shota Ikebe, Shigeaki Yamazaki, Masashi Ishikawa ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 99 PUBLICATIONS Nonaqueous gel electrolytes based on chitosan and 1-ethyl-3-methylimidazolim tetrafluoroborate (Chi/EMImBF4) are prepared for electric double-layer capacitors (EDLCs). The transparent colorless gel sheet has the high levels of mechanical strength and ionic liquid retention required in EDLC cells. Charge– discharge measurements revealed that a model EDLC cell with a chitosan gel exhibits high discharge capacitance although a gel-state electrolyte was used, indicating that the high affinity of chitosan for the activated carbon electrode decreases the electrode–electrolyte interfacial resistance. A test cell with Chi/EMImBF4 maintained a Coulombic efficiency of more than 99.9% during 5000 cycles. Composition and structure of Al–Sn alloys formed by constant potential electrolysis in an AlCl3–NaCl–KCl–SnCl2 molten salt Electrochimica Acta, 100, 2013, 281-284 Mikito Ueda, Ryuichi Inaba, Toshiaki Ohtsuka To form Al–Sn alloys for bearing materials, molten salt electrolysis was performed in an AlCl3–NaCl–KCl molten salt containing SnCl2 at 423 K. The voltammogram showed that the cathodic reduction of the Sn ions started at a potential of 0.5 V vs. Al/Al(III) in the molten salt showing that deposition of pure Sn was possible at 0.5 V. Co-deposition of Al and Sn occurred at potentials more negative than 0.1 V. The co-deposit was composed a solid solution of Al and Sn. The ratio of the Sn in the electrodeposits decreased with the potential from 100 at.% at 0.2 V to 19 at.% at −0.3 V. In the structural observations, electrodeposits with an alternate stacked structure of Al and Sn is obtained at −0.075 V. Physicochemical properties of 1-alkyl-3-methylimidazolium chloride–urea melts Electrochimica Acta, 100, 2013, 285-292 Tetsuya Tsuda, Koshiro Kondo, Masahiro Baba, Shotaro Suwa, Yuichi Ikeda, Taiki Sakamoto, Satoshi Seino, Hiroyuki Yoshida, Masanori Ozaki, Akihito Imanishi, Susumu Kuwabata Physicochemical data of the novel low-melting-point melt systems combining urea with the 1-alkyl-3-methylimidazolium chloride ([R1MeIm]Cl) were examined in order to produce an alternative to room-temperature ionic liquid that is very expensive to prepare and purify compared to the conventional molecular solvents. [HexMeIm]Cl- and [MeOctIm]Cl-rich urea melts, which have almost the same pyrolysis temperature as neat [HexMeIm]Cl and [MeOctIm]Cl organic salts, showed a stable liquid phase at room temperature. The various physicochemical properties of the [MeOctIm]Cl-rich urea room-temperature melts were measured as a function of temperature. The VTF equation was fitted to the conductivity and viscosity data, and a simple polynomial was fitted to the density data. Interestingly, although the 75.0–25.0 mol% [BuMeIm]Cl–urea ___________________________________________________________________________ page 100 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS melt did not give a stable liquid phase at room temperature, the melt showed favorable conductivity that exceeds that for the [MeOctIm]Cl-rich urea melts at the temperature exceeding 323 K. Further investigation on the applications, e.g., Cu electroplating, SEM observation technique, and Au nanoparticle preparation, using the [R1MeIm]Cl–urea melt system revealed that the melt system has a great possibility as an alternative to the RTIL. CO2 gas decomposition to carbon by electro-reduction in molten salts Electrochimica Acta, 100, 2013, 293-299 Koya Otake, Hiroshi Kinoshita, Tatsuya Kikuchi, Ryosuke O. Suzuki The electrochemical decomposition of CO2 gas in LiCl–Li2O or CaCl2–CaO molten salt was studied to produce carbon. This process consists of the electrochemical reduction of the oxide, Li2O or CaO, and the thermal reduction of CO2 gas by metallic Li or Ca. Two kinds of ZrO2 solid electrolytes were tested as an oxygen ions conductor and removed oxygen ions from the molten salts to the outside of reactor. After the electrolysis in the both salts, the aggregations of nanometer-scale amorphous carbon and rod-like graphite crystals were observed by transmission electron microscope. When 9.7% CO2– Ar mixed gas was blown into LiCl–Li2O or CaCl2–CaO molten salt, the current efficiency was evaluated to be 89.7% or 78.5%, respectively, by the exhaust gas analysis and the supplied charge. When the solid electrolyte with the better ionic conductivity was used, the current and the carbon production became larger. The rate determining step of this proposal was diffusion of oxygen ions in ZrO2 solid electrolyte. Formation of metallic Si and SiC nanoparticles from SiO2 particles by plasma-induced cathodic discharge electrolysis in chloride melt Electrochimica Acta, 100, 2013, 300-303 M. Tokushige, H. Tsujimura, T. Nishikiori, Y. Ito Silicon nanoparticles are formed from SiO2 particles by conducting plasmainduced cathodic discharge electrolysis. In a LiCl–KCl melt in which SiO2 particles were suspended at 450 °C, we obtained Si nanoparticles with diameters around 20 nm. During the electrolysis period, SiO2 particles are directly reduced by discharge electrons on the surface of the melt just under the discharge, and the deposited Si atom clusters form Si nanoparticles, which leave the surface of the original SiO2 particle due to free spaces caused by a molar difference between SiO2 and Si. We also found that SiC nanoparticles can be obtained using carbon anode. Based on Faraday's law, the current efficiency for the formation of Si nanoparticles is 70%. Optical observation of Li dendrite growth in ionic liquid Electrochimica Acta, 100, 2013, 333-341 T. Nishida, K. Nishikawa, M. Rosso, Y. Fukunaka ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 101 PUBLICATIONS The electrodeposition process of Li metal in 1.0 M LiTFSI–ionic liquid (Nmethoxymethyl-N-methylpyrrolidinium) bis(trifluoromethane-sulfonyl) imide was observed in situ by optical microscope. Morphological variations of electrodeposited Li dendrite and its growth rate were examined and the ionic mass transfer rate in the vicinity of the electrode surface was discussed. Once the dendrite starts to grow, its length is proportional to the square root of time. This indicates that the Li+ mass transfer rate affects its growth. Dendrite growth process can be classified into two regions depending on its growth rate: the initiation period and the growing period with swinging behavior probably caused by residual stress. Electrodeposition of metals in microgravity conditions Electrochimica Acta, 100, 2013, 342-349 Kei Nishikawa, Yasuhiro Fukunaka, Elisabeth Chassaing, Michel Rosso Metal electrodeposition may produce irregular deposits with various morphologies. For liquid electrolytes a precise study of these deposits may be complicated by convective motion due to buoyancy. Microgravity conditions give a straightforward mean to avoid this effect: we present here a study of electrodeposition in the microgravity environment provided by parabolic flights. Two electrochemical systems were studied: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. Concentration variations in the electrolyte were measured by laser interferometry. For copper, concentration variations were in good agreement with theory. For lithium, an induction time was observed for the concentration evolution in ground experiments: due to this induction time and to the low diffusion coefficient in ionic liquid, concentration variations were hardly measurable during the 20 s parabolic flight.. Effects of marine atmosphere on the cell performance in molten carbonate fuel cells Journal of Power Sources, 232, 2013, 17-22 Shin Ae Song, Hyun Koo Kim, Hyung Chul Ham, Jonghee Han, Suk Woo Nam, Sung Pil Yoon The effects of NaCl, a main component in seawater, on molten carbonate fuel cell (MCFC) performance is investigated using a single cell test with 1, 5, and 10 wt.% NaCl-impregnated cathodes for marine applications. The cell performance increases with increasing amounts of impregnated NaCl in the cathode. This cell performance enhancement is due to the reduction in the charge transfer resistance of the electrode. From the analysis of the electrolyte composition using the inductively coupled plasma (ICP) and ion chromatography (IC) methods after cell operation, it is confirmed that the Na+ ___________________________________________________________________________ page 102 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS ions are accumulated in the carbonate melts, and approximately 80 at.% of the Cl- ions are emitted into the anode outlet as HCl. Expecting that the emitted HCl causes severe corrosion of the utilities, the concentrations of accumulated Na+ ions of emitted HCl in the anode outlet are calculated when air with a sea-salt particle concentration of 5–500 ugm−3 is supplied to the MCFC stack. Although HCl is a very corrosive gas, it is expected that the emitted HCl does not cause severe corrosion because, even at a high sea-salt concentration of 500 ugm−3, the emitted HCl concentration is low enough to operate the stack safely. Exploring sulfur solubility in ionic liquids for the electrodeposition of sulfide films with their electrochemical reactivity toward lithium Electrochimica Acta, 99, 2013, 46-53 Yunhua Chen, Jean-Marie Tarascon, Claude Guéry Metal binary sulfides (TiS2, FeS2), in either powder or thin film forms, were the first studied Li insertion electrodes for rechargeable lithium batteries, with thin films made mainly by sputtering. Here we exploit the equilibrium solubility of molecular sulfur into ionic liquids at its melting point (120 °C), which we estimated to be at a maximum level of 80 mM by both electrochemical and microwave studies, to prepare thin films of both Co9S8 and FeSx showing initial capacities of 559 mAh g−1 and 708 mAh g−1 versus lithium in coin cells, respectively. We demonstrate that the growth of Co9S8 films involves the reaction of soluble sulfur with the electrodeposited Co metallic layer, while the formation of FeSx films enlists a precipitation between the reduced Fe(II) cations and the electrochemically produced Sxy− species in the ionic liquid bath. Such findings, namely the solubility of sulfur into ionic liquids, open opportunities to electrodeposit sulfur-based compounds as well as capture sulfur from various media enabling a better environment. Water-soluble, triflate-based, pyrrolidinium ionic liquids Electrochimica Acta, 99, 2013, 108-116 M. Moreno, M. Montanino, M. Carewska, G.B. Appetecchi, S. Jeremias, S. Passerini The physicochemical and electrochemical properties of the water-soluble, Nmethoxyethyl-N-methylpyrrolidinium trifluoromethanesulfonate (PYR1(2O1)OSO2CF3) ionic liquid (IL) were investigated and compared with those of commercial N-butyl-N-methylpyrrolidinium trifluoromethanesulfonate (PYR14OSO2CF3). The results have shown that the transport properties are well correlated with the rheological and thermal behavior. The incorporation of an oxygen atom in the pyrrolidinium cation aliphatic side chain resulted in enhanced flexibility of the ether side chain, this supporting for the higher ionic conductivity, self-diffusion coefficient and density of PYR1(2O1)OSO2CF3 with respect to PYR14OSO2CF3, whereas no relevant effect on the crystallization of ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 103 PUBLICATIONS the ionic liquid was found. Finally, the presence of the ether side chain material in the pyrrolidinium cation led to a reduction in electrochemical stability, particularly on the cathodic verse. New hydrophobic ionic liquids based on (fluorosulfonyl)(polyfluorooxaalkanesulfonyl)imides with various oniums Electrochimica Acta, 99, 2013, 262-272 Chengyong Liu, Fei Xu, Shaowei Feng, Liping Zheng, Heng Zhang, Wenfang Feng, Xuejie Huang, Michel Armand, Jin Nie, Zhibin Zhou Sixteen ionic liquids (ILs) based on two new asymmetric imide anions, (fluorosulfonyl)(polyfluorooxaalkanesulfonyl)imide {[(FSO2)(XCF2CF2OCF2CF2SO2)N]−, [5X3O-FOFSI]−, X = H and I}, are synthesized and characterized by in combination with various oniums, including 1,3-dialkylimidazolium, quaternary alkyl (or ether-functionalized alkyl)ammonium, N-alkyl-N-methyl-pyrrolidinium and -piperidinium. Their physicochemical properties are investigated, in terms of phase transitions, thermal stability, density, viscosity, ionic conductivity, electrochemical stability, and the capability as electrolytes to allow Li deposition/stripping. The influences of the structural variations in both the cations and anions, particularly introduction of an ether group into the anion, on the above properties are systematically studied. All the ILs are liquids at room temperature and show low glass transition temperatures, suggesting the high flexibility of the etherfunctionalized imide anion. It has been demonstrated that only having an ether group into the polyfluoroalkyl chain of the imide anion affect neither the cathodic nor anodic stability of the anion and their ILs. The ILs based on the [5H3O-FOFSI]− anion have an enough electrochemical stability to allow Li deposition/striping, while those based on the [5I3O-FOFSI]− anion show relatively low cathodic stability due to the presence of a CI bond in the anion. Preparation and evaluation of cellulose-dissolving magnetic ionic liquid Journal of Molecular Liquids, 182, 2013, 76-78 Jin Muraoka, Noriho Kamiya, Yuji Ito Ionic liquids have attracted attention as potential pretreatment agents in cellulosic biomass processing. Here we report on a new magnetic ionic liquid that can dissolve crystalline cellulose and be collected by a magnet. Solid lithium electrolyte-Li4Ti5O12 composites as anodes of lithium-ion batteries showing high-rate performance Journal of Power Sources, 231, 2013, 177-185 Yujing Sha, Tao Yuan, Bote Zhao, Rui Cai, Huanting Wang, Zongping Shao A new concept lithium-ion conducting lithium lanthanum titanate solid electrolyte and Li4Ti5O12 composite is proposed as efficient anode of lithium-ion ___________________________________________________________________________ page 104 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS batteries with outstanding rate performance, which can be facilely prepared by one-pot combustion technique. The as-synthesized composites are in micrometer size with dense nature which effectively reduces the electrode-liquid electrolyte interface area, thus decreasing irreversible capacity during the first charge– discharge cycle and prolonging cycling stability. However, the composites are rich in lithium lanthanum titanate and Li4Ti5O12 dual phase boundaries due to intimate nanoscale mixing of the two phases. The apparent lithium-ion conductivity of the composite electrode gets significantly improved as compared to pristine Li4Ti5O12 due to the incorporation of lithium lanthanum titanate phase, a high lithium ionic conductor. As a result, the as-synthesized composites show a high capacity of 113.5 mA h g−1 even at a discharge rate of 40 C, more than 200% that of a pristine Li4Ti5O12. The concept is general, which may also be applicable to other electrode materials, and it thus introduces a new way for the development of high rate-performance electrodes for lithium-ion batteries. The compressibility of molten salts The Journal of Chemical Thermodynamics, 61, 2013, 7-10 Yizhak Marcus Values of the adiabatic and isothermal compressibility, κS and κT, of some 80 molten salts at the corresponding temperature of T = 1.1Tm (Tm is the melting point) are obtained from literature data either directly or re-calculated here. For some of the series of salts: alkali metal halides and nitrates, divalent metal halides, and alkali metal sulfates and carbonates the κT values are inversely proportional to the corresponding cohesive energy densities ced (internal energies per unit volume, separately for each class of compounds). The ced values for 1:2 and 2:1 salts not previously evaluated are presented here too. Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction The Journal of Chemical Thermodynamics, 61, 2013, 32-44 Yvon Rodrigue Dougassa, Cécile Tessier, Loubna El Ouatani, Mérièm Anouti, Johan Jacquemin We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 105 PUBLICATIONS predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm−3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure. Phase behaviour at different temperatures of an aqueous two-phase ionic liquid containing ([Bmim]BF4 + manganese sulfate + water) The Journal of Chemical Thermodynamics, 61, 2013, 45-50 Bruno Giordano Alvarenga, Luciano Sindra Virtuoso, Nelson Henrique Teixeira Lemes, Pedro Orival Luccas The phase diagrams and liquid + liquid equilibrium (LLE) data of the 1-butyl-3methylimidazolium tetrafluoroborate {([Bmim]BF4) + Manganese sulfate (MnSO4) + water} system have been determined experimentally at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K. As the temperature decreases, this aqueous two-phase system exhibits a phase inversion. Specifically, the [Bmim]BF4-rich phases are the less dense top phases at high temperatures but become the bottom phase at elevated temperatures. The effect depends on the concentration of both the [Bmim]BF4 and MnSO4. At temperatures of (293.15 and 303.15) K, inversion occurs for the system only at higher concentrations of either phase-forming constituent. In addition, as the temperature increases the inversion-phase region expands. The binodal curves are fitted to an empirical non-linear expression developed by Merchuk, and the salting-out effect at various temperatures was studied quantitatively using the Setschenow equation. Osmotic and apparent molar properties of binary mixtures alcohol + 1butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid The Journal of Chemical Thermodynamics, 61, 2013, 64-73 Emilio J. González, Noelia Calvar, Ángeles Domínguez, Eugénia A. Macedo ___________________________________________________________________________ page 106 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS In this work, physical properties (densities and speeds of sound) for the binary systems {1-propanol, or 2-propanol, or 1-butanol, or 2-butanol, or 1pentanol + 1-butyl-3-methylimidazolium trifluoromethanesulfonate} were experimentally measured from T = (293.15 to 323.15) K and at atmospheric pressure. These data were used to calculate the apparent molar and apparent molar isentropic compression which were fitted to a Redlich–Meyer type equation. This fit was used to obtain the corresponding apparent molar properties at infinite dilution. On the other hand, the osmotic and activity coefficients and vapor pressures of these binary mixtures were also determined at T = 323.15 K using the vapor pressure osmometry technique. The Extended Pitzer model of Archer was employed to correlate the experimental osmotic coefficients. From the parameters obtained in the correlation, the mean molal activity coefficients and the excess Gibbs free energy for the studied mixtures were calculated. Separation of thiophene from heptane with ionic liquids The Journal of Chemical Thermodynamics, 61, 2013, 126-131 Urszula Domańska, Elena Vadimovna Lukoshko, Marek Królikowski Ionic liquids (ILs) are well known novel green solvents, which can be used for removing sulfur compounds from gasoline and diesel oils. Ternary (liquid + liquid) equilibrium data are presented for mixtures of {ionic liquid (1) + thiophene (2) + heptane (3)} at T = 298.15 K and ambient pressure to analyze the performance of the ionic liquid (IL) in the extraction of thiophene from the alkanes. Three pyrrolidinium-based ionic liquids have been studied: 1butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, ([BMPYR][FAP]), 1-butyl-1-methylpyrrolidinium tetracyanoborate, [BMPYR][TCB] and 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM]. The results are discussed in terms of the selectivity and distribution ratio of separation of related systems. The immiscibility in the binary liquid systems of (thiophene + heptane) with all used ILs was observed. The [TCM]− anion in comparison with [TCB]− and [FAP]− anions shows much higher selectivity and slightly lower distribution ratio for extraction of thiophene. The non-random two liquid NRTL model was used successfully to correlate the experimental tie-lines and to calculate the phase composition error in mole fraction in the ternary systems. The average root mean square deviation (RMSD) of the phase composition was 0.047. The densities of [BMPYR][TCM] in temperature range from (298.15 to 348.15) K were measured. The data presented here show that the [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the hydrocarbon stream using solvent liquid–liquid extraction at ambient conditions. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 107 PUBLICATIONS Cathodic behaviour and oxoacidity reactions of samarium (III) in two molten chlorides with different acidity properties: The eutectic LiCl–KCl and the equimolar CaCl2–NaCl melt Electrochimica Acta, 97, 2013, 120-131 Y. Castrillejo, C. de la Fuente, M. Vega, F. de la Rosa, R. Pardo, E. Barrado This work presents a study on the chemical and electrochemical properties of Sm(III) solutions in two molten chloride mixtures with different acidity properties: (i) the eutectic LiCl–KCl, in the temperature range 673–823 K and (ii) the equimolar CaCl2–NaCl melt at 823 K. In both media and on a W inert electrode, the electro-reduction of Sm(III) takes place via one step Sm(III)/Sm(II). The second system Sm(II)/Sm(0) has not been observed within the electrochemical windows, because of the prior reduction of Li(I) and Na(I) from the solvent, which inhibits the electro-extraction of Sm species from the salts on the inert substrate. On the W electrode, the electro-reduction of Sm(III) to Sm(II) takes place in a quasi-reversible electrochemical mode. Accurate values of the reversible half wave potential, the intrinsic rate constant of charge transfer, k0, and the charge transfer coefficient, α, have been calculated for the first time in both molten chlorides, by simulation of the cyclic voltammograms and logarithmic analysis of the convoluted curves. The diffusion coefficient of Sm(III) has been also calculated by different electrochemical techniques, avoiding the meniscus effect by modification of the immersion dept of the working electrode in stages. The values of the diffusion coefficient indicate that Sm(III) diffuses slower in the equimolar CaCl2–NaCl than in the eutectic LiCl–KCl. This behaviour can be explained by the different viscosities of both media, which significantly reduces the mobility of Sm(III) in the CaCl2–NaCl melt.The identification of the Sm-O compounds that are stable in the melts as well as the determination of their solubility products were carried out by potentiometric titration using an yttria stabilised zirconia membrane electrode (YSZME). The results indicated that SmOCl is a solid stable compound in the studied melts and that Sm2O3 is a strong oxobase leading to the formation of SmOCl. The best chlorination conditions have been extracted from the comparison of the E-pO2− diagram of samarium and that of some gaseous chlorinating mixtures previously reported. The state of water in 1-butly-1-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide and its effect on Zn/Zn(II) redox behavior Electrochimica Acta, 97, 2013, 289-295 M. Xu, D.G. Ivey, Z. Xie, W. Qu, E. Dy Water was added as a diluent into the hydrophobic room temperature ionic liquid (RTIL) 1-butly-1-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) with the purpose of improving the conductivity of the RTIL, which ___________________________________________________________________________ page 108 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS is being considered as a potential electrolyte for rechargeable Zn-air batteries. The behavior of water additions in BMP-TFSI and its effect on Zn/Zn(II) redox behavior in BMP-TFSI were studied. Two types of water, free or unbound water and bound water, were identified in BMP-TFSI through DSC and FTIR analysis and density functional theory (DFT) modeling. When the water content was less than ~2.0 wt%, water molecules interacted with [TFSI]− anions through hydrogen bonding. When the water amount was greater than 2.0 wt%, clusters of water molecules (free water) were observed. Bound water in BMP-TFSI improved Zn/Zn(II) redox reversibility by reducing the activation overpotential for electrochemical reactions. The optimal amount of water, in terms of the kinetic properties for Zn/Zn(II) redox in BMP-TFSI, was 2.0 wt%. Compared with water-free BMP-TFSI, both the diffusion coefficient for the Zn species and the exchange current density for Zn/Zn(II) redox reactions increased by approximately 70% in BMP-TFSI with 2.0 wt% water addition. Electrochemical behavior of morphine at ZnO/CNT nanocomposite room temperature ionic liquid modified carbon paste electrode and its determination in real samples Journal of Molecular Liquids, 181, 2013, 8-13 Elahe Afsharmanesh, Hassan Karimi-Maleh, Ali Pahlavan, Javad Vahedi In this paper we report synthesis and application of ZnO/CNT nanocomposite and 1-methyl-3-butylimidazolium bromide as high sensitive sensors for voltammetric determination of morphine using carbon paste electrode. The ZnO/CNT nanocomposite was characterized with different methods such as TEM, SEM and XRD. The electrochemical oxidation of morphine on the new ZnO/CNTs ionic liquid carbon paste electrode (ZnO/CNTs/IL/CPE) was carefully studied. The oxidation peak potential of morphine on the ZnO/CNTs/IL/CPE appeared at 520 mV, which was about 75 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about 5.5 times. The electrochemical parameter of morphine on the ZnO/CNTs/IL/CPE was calculated with the charge transfer coefficient (α). Based on the relationship of the oxidation peak current and the concentration of morphine a sensitive analytical method was established with cyclic voltammetry. The linear range for morphine determination was in the range from 0.1 to 700 µmol L− 1 and the detection limit was calculated as 0.06 µmol L− 1 (3σ). Finally, the proposed method was also examined as a selective, simple and precise electrochemical sensor for the determination of morphine in real samples such as urine and ampoule. An investigation of the reaction between 1-butyl-3-methylimidazolium trifluoromethanesulfonate and superoxide ion Journal of Molecular Liquids, 181, 2013, 44-50 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 109 PUBLICATIONS Maan Hayyan, Farouq S. Mjalli, Mohd Ali Hashim, Inas M. AlNashef Superoxide ion (O2−) generation in ionic liquids (ILs) has been investigated recently using various types of ILs. Imidazolium based ILs are the most frequently studied ILs. In this work, O2− was generated and analyzed electrochemically using cyclic voltammetry and chronoamperometry techniques from O2 dissolved in 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIm][TfO]. Furthermore, O2− was generated chemically by potassium superoxide addition into the same IL. UV/Vis spectrophotometry was utilized for testing the long term stability of the generated O2− and GC/MS was used to investigate the possible reaction between the generated O2− and [BMIm][TfO]. The results showed that O2− was unstable in this IL. The GC/MS results confirmed that O2− has reacted with [BMIm][TfO] producing 1-butyl-3-methyl2-imidazolone in a high purity and excellent yield. This product and its family are used widely in various applications and have a very important role in pharmacology and chemotherapy. Incorporation of benzimidazolium ionic liquid in proton exchange membranes ABPBI-H3PO4 Journal of Molecular Liquids, 181, 2013, 115-120 Rubí Hernández Carrillo, Jullieth Suarez-Guevara, Luis Carlos Torres-González, Pedro Gómez-Romero, Eduardo M. Sánchez This paper presents the development of proton exchange membranes (PEM) from the incorporation of poly (2,5-benzimidazole) (ABPBI) in phosphoric acid (H3PO4) and ionic liquid (IL) 1-butyl-3-ethylbenzimidazolium dihydrogen phosphate (BEBzIm-H2PO4). We show structural, physicochemical and electrochemical characterization of synthesized IL and prepared membranes. The addition of IL in composite membranes of ABPBI-H3PO4 increases thermal stability. Also, the conductivity of membranes increases with temperature and the amount of absorbed mixture. Conductivity at a range of 10− 4 S/cm was achieved at 150 °C by 50% IL and 50% phosphoric acid impregnation. This conducting composite membrane shows promise for operation in temperature proton exchange membrane fuel cells at working temperatures up to 100 °C. Exploring physicochemical aspects of N-alkylimidazolium based ionic liquids Journal of Molecular Liquids, 181, 2013, 142-151 Mohsin Ahmad Bhat, Chanmeet K. Dutta, Ghulam Mohammad Rather Physicochemical aspects (structural, thermodynamic and transport) of 1-butyl-3methylimidazolium tetrafluoroborate ([BMIM][BF4]), 1-butyl-2,3dimethylimidazolium tetrafluoroborate ([BDMIM][BF4]) and 1-butyl-3methylimidazolium hexafluorophosphate ([BMIM][PF6]) room temperature ionic liquids (RTILs) are reported. The results based on temperature dependence ___________________________________________________________________________ page 110 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS of surface tension, conductivity, photoluminescence and spectroscopic measurements on RTILs and their mixtures with acetonitrile (ACN) as cosolvent are interpreted in-terms of structure–composition–property relations. The presented observations clearly indicate that a highly structured and organized arrangement of constituents prevails in the investigated RTILs, which is sensitive to temperature variations and cosolvent addition. Thermodynamic and structural parameters estimated from temperature dependency of interfacial tension demonstrate that surface characteristics are dominated by covalent interactions in imidazolium based RTILs. From composition dependence of measured parameters in RTIL–cosolvent mixtures it is shown that ACN mixes nonideally with RTIL, and interestingly the investigated RTILs retain their inherent structural order up to high dilution limits (0.3 fraction of RTIL), beyond which these behave as associated electrolytes. The presented findings seem useful for arriving at molecular basis of physicochemical aspects and future applications of RTILs and their binary mixtures especially with cosolvents for biphasic catalysis and heterogeneous electron transfer reactions, wherein temperature elevation and cosolvent addition are currently advocated as operationally simple means to speed up the mass transport. (Liquid + liquid) equilibria for (cholinium-based ionic liquids + polymers) aqueous two-phase systems The Journal of Chemical Thermodynamics, 60, 2013, 1-8 Xinxin Liu, Zhiyong Li, Yuanchao Pei, Huiyong Wang, Jianji Wang Searching for environmentally friendly aqueous two-phase systems is imperative for the sustainable development of bioseparation technologies. In the present work, (liquid + liquid) equilibrium data have been determined experimentally for aqueous two-phase systems formed by the cholinium-based ionic liquids (cholinium glycollate, cholinium propionate, cholinium lactate, and choline chloride) and polymers {polypropylene glycol 400 (PPG400), polypropylene glycol 1000 (PPG1000), and poly(ethylene glycol)-block-poly(propylene glycol)-poly(ethylene glycol) (EO10PO90)}. The effects of anion type of the ionic liquids, the nature of the polymers and temperature of the systems are examined on the phase-forming capacity of the systems. Then the binodal results have been satisfactorily fitted to a three-parameter empirical equation. The tie-line data are well described by the Othmer–Tobias and Bancroft equations. Application of 1-alkyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide ionic liquids for the ethanol removal from its mixtures with alkanes The Journal of Chemical Thermodynamics, 60, 2013, 9-14 Begoña González, Sandra Corderí, Alberto G. Santamaría ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 111 PUBLICATIONS In this work, two ionic liquids 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, [EMpy][NTf2], and 1-methyl-3propylpyridinium bis(trifluoromethylsulfonyl)imide, [PMpy][NTf2], were investigated as possible solvents in the extraction processes for the ethanol removal from its mixtures with heptane and hexane. Hence, the experimental determination of the (liquid + liquid) equilibrium (LLE) for the ternary systems {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} at T = 298.15 K and atmospheric pressure was carried out. The solute distribution ratio and selectivity were calculated to evaluate the capability of these ionic liquids for the extraction of ethanol. Moreover, comparisons with other ILs taken from the literature were made. Finally, the experimental LLE values were compared with the correlated values obtained by means of the NRTL thermodynamic model. Aggregation behaviour and thermodynamics of mixed micellization of gemini surfactants with a room temperature ionic liquid in water and water-organic solvent mixed media The Journal of Chemical Thermodynamics, 60, 2013, 29-40 Amit K. Tiwari, Sonu, Subit K. Saha Aggregation behaviour and thermodynamics of mixed micellization of two cationic gemini surfactants, 1,3-bis(dodecyl-N,N-dimethylammonium bromide)2-propanol [12-3(OH)-12,2Br−] and 1,4-bis(dodecyl-N,N-dimethylammonium bromide)-2,3-butanediol [12-4(OH)2-12,2Br−] with a room temperature ionic liquid (RTIL), 1-dodecyl-3-methylimidazolium bromide (DMIL) in water and in binary mixed media of water and organic solvents [1,4-dioxane (DO) and ethylene glycol (EG)] have been investigated by means of conductivity, fluorescence and dynamic light scattering measurements at T = 303.15 K. The chemical nature of the spacer groups of gemini surfactants and the organic cosolvents have significant effect on the aggregation behaviour and the thermodynamics of mixed micellization. The mixed micellization behaviour with possible interactions between DMIL and 12-3(OH)-12,2Br−/12-4(OH)212,2Br− have been demonstrated. The process of micellization of DMIL + 124(OH)2-12,2Br− is comparatively delayed than that of DMIL + 12-3(OH)12,2Br− in a given solvent system. The micellization process is progressively delayed with increasing bulk mole fraction of DMIL (αDMIL). The hydrodynamic diameter of DMIL + 12-4(OH)2-12,2Br− micelle is smaller than that of DMIL + 12-3(OH)-12,2Br− micelle. The micellar mole fraction of DMIL estimated using different theories (Rubingh, Rodenas and Motomura) is higher than that expected for an ideal system. The attractive interactions among the mixed micellar components are described on the basis of Rubingh’s β parameter, activity coefficient values, experimental and ideal cmc values, and the values of micellar mole fractions. The negative values of excess Gibbs energy (GE) in ___________________________________________________________________________ page 112 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS aqueous and mixed solvent media indicate that the non-ideal mixed micellar systems are more stable than the corresponding ideal systems. A micelle structure becomes more open when the dielectric constant (ε) of the solvent is reduced. Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(2-methoxyethyl)-1methylpyrrolidinium trifluorotris(perfluoroethyl)phosphate The Journal of Chemical Thermodynamics, 60, 2013, 57-62 Andrzej Marciniak, Michał Wlazło This work presents new data of activity coefficients at infinite dilution, γ∞ of different organic solutes and water in the 1-(2-methoxyethyl)-1methylpyrrolidinium trifluorotris(perfluoroethyl)phosphate ionic liquid. Values of γ∞ were determined for 62 solutes, including alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, 1-nitropropane, butanal, acetonitrile and water by inverse gas chromatography over the temperature range from (318.15 to 368.15) K. The basic thermodynamic functions, namely partial molar excess Gibbs energies, , enthalpies, and entropies, at infinite dilution were calculated from the experimental γ∞ values obtained over the temperature range. Additionally the gas–liquid partition coefficients, KL were determined. Experimental values of gas–liquid partition coefficients were used to determine the coefficients in the Abraham solvation parameter model (LFER). Results are compared to previously investigated ionic liquids with the same cations or anions. The selectivities and capacities at infinite dilution for alkanes/thiophene extraction problems were calculated from experimental γ∞ values to verify the possibility of investigated ionic liquid as an entrainer in liquid–liquid extraction. Thermodynamic properties of binary mixtures of the ionic liquid [emim][BF4] with acetone and dimethylsulphoxide The Journal of Chemical Thermodynamics, 60, 2013, 76-86 S. Bhagour, S. Solanki, N. Hooda, D. Sharma, V.K. Sharma The densities, ρ, speeds of sound, u of 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + acetone or dimethylsulphoxide (j) binary mixtures at T/K = (293.15, 298.15, 303.15, 308.15) and excess molar enthalpies, HE of the same mixtures at T/K = (298.15) have been measured over entire mole fraction using DSA-5000 and 2-drop microcalorimeter respectively. The measured data have been utilized to calculate excess molar volumes, VE and excess isentropic compressibilities, . The Graph theory (which deals with topology of the constituents of mixtures) has been applied to calculate (i) state of components of ionic liquid mixtures in their pure and mixed state; (ii) nature and extent of interactions existing in mixtures; and (iii) VE, HE and values. Topological ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 113 PUBLICATIONS investigation of VE data in terms of Graph theory suggest that while 1-ethyl-3methylimidazolium tetrafluoroborate is characterized by ionic attraction and exist as monomer; acetone or dimethylsulphoxide exist as associated molecular entities. Further, 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + acetone or dimethylsulphoxide (j) mixtures are characterized by interactions between hydrogen atom of (C-2) of [emim]+ cation with oxygen atom of acetone or dimethylsulphoxide and fluorine atom of [BF4]− anion with carbon atom of acetone or sulphur atom of dimethylsulphoxide. The IR studies lend additional support to the nature and extend of interactions in the studied mixtures. The VE, HE and values calculated by Graph theory compare well with their corresponding experimental values and PFP theory correctly calculate the sign of VE, HE and values of the studied mixtures. Experimental and theoretical study on infinite dilution activity coefficients of various solutes in piperidinium ionic liquids The Journal of Chemical Thermodynamics, 60, 2013, 169-178 Kamil Paduszyński, Urszula Domańska The aim of this work is to summarize our systematic studies on activity coefficients at infinite dilution () of various organic compounds and water in 1n-alkyl-1-methylpiperidinium cation-based ionic liquids with bis[(trifluoromethyl)sulfonyl]imide anion, [CnC1Pip][NTf2] (n = 3–6). New sets of experimental data measured by gas-liquid chromatography are reported for 43 different solutes in [C5C1Pip][NTf2] and [C6C1Pip][NTf2] in temperature range to K. Moreover, ambient pressure liquid densities of those ionic liquids are presented at different temperatures. The results are discussed in terms of an influence of structure of both solute and ionic liquid on . Capabilities of the studied ionic liquids in liquid-liquid extraction of aromatics or sulphur compounds from aliphatic hydrocarbons are demonstrated in terms of infinite dilution selectivity and capacity. Finally, linear solvation energy relationship (LSER) theory and regular solution theory (RST) were used to analyze the obtained experimental data. In particular, correlative and predictive power of the most current version of the LSER is demonstrated and the Hildebrand’s solubility parameters are calculated as a function of temperature by using the RST. Water-based synthesis of hydrophobic ionic liquids for high-energy electrochemical devices Electrochimica Acta, 96, 30 April 2013, 124-133 Maria Montanino, Fabrizio Alessandrini, Stefano Passerini, Giovanni Battista Appetecchi In this work is described an innovative synthesis route for hydrophobic ionic liquids (ILs) composed of N-methyl-N-alkylpyrrolidinium (or piperidinium) or ___________________________________________________________________________ page 114 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS imidazolium or tetralkylammonium cations and (perfluoroalkylsulfonyl)imide, ((CnF2n+1SO2)(CmF2m+1SO2)N−), anions. This synthesis does not require the use of any environmental unfriendly solvent such as acetone, acetonitrile or halogen-containing compounds, which is not welcome in industrial applications. Only water is used as the process solvent throughout the entire process. In addition, the commonly used iodine-containing reagents were replaced by the cheaper, more chemically stable and less toxic bromine-containing compounds. A particular care was devoted to the development of the purification route, which is especially important for ILs to be used in high-energy electrochemical devices such as high voltage supercapacitors and lithium batteries. The effect of the reaction temperature, the time and the stoichiometry in the various steps of the synthesis have been investigated in detail. This novel procedure allowed obtaining ultrapure (>99.9 wt.%), clear, colourless, inodorous ILs with an overall yield above 92 wt.% and moisture content below 1 ppm. NMR measurements were run to confirm the chemical structure whereas elemental analysis and electrochemical tests were performed to check the purity of the synthesized ILs. Microwave-assisted ionothermal synthesis of nanostructured anatase titanium dioxide/activated carbon composite as electrode material for capacitive deionization Electrochimica Acta, 96, 30 April 2013, 173-179 Po-I Liu, Li-Ching Chung, Hsin Shao, Teh-Ming Liang, Ren-Yang Horng, Chen-Chi M. Ma, Min-Chao Chang The nanostructured anatase titanium dioxide/activated carbon composite material for capacitive deionization electrode was prepared in a short time by a lower temperature two-step microwave-assisted ionothermal (sol–gel method in the presence of ionic liquid) synthesis method. This method includes a reaction and a crystallization step. In the crystallization step, the ionic liquid plays a hydrothermal analogy role in driving the surface anatase crystallization of amorphous titanium dioxide nanoparticles formed in the reaction step. The energy dispersive spectroscopic study of the composite indicates that the anatase titanium dioxide nanoparticles are evenly deposited in the matrix of activated carbon. The electrochemical property of the composite electrode was investigated. In comparison to the pristine activated carbon electrode, higher specific capacitance was observed for the nanostructured anatase titanium dioxide/activated carbon composite electrode, especially when the composite was prepared with a molar ratio of titanium tetraisopropoxide/H2O equal to 1:15. Its X-ray photoelectron spectroscopic result indicates that it has the highest amount of Ti-OH. The Ti-OH group can enhance the wetting ability and the specific capacitance of the composite electrode. The accompanying capacitive deionization result indicates that the decay of electrosorption capacity of this ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 115 PUBLICATIONS composite electrode is insignificant after five cycle tests. It means that the ion electrosorption–desorption becomes a reversible process. One-step wet chemical deposition of NiO from the electrochemical reduction of nitrates in ionic liquid based electrolytes Electrochimica Acta, 96, 30 April 2013, 261-267 Eneko Azaceta, Ngo Thi Tuyen, David F. Pickup, Celia Rogero, J. Enrique Ortega, Oscar Miguel, Hans-Jurgen Grande, Ramon Tena-Zaera Aprotic PYR14TFSI (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)) ionic liquid served to develop a new electrochemical route for one-step deposition of NiO from PYR14NO3 reduction (1-butyl-1-methylpyrrolidinium nitrate) in a Ni(TFSI)2 (Nickel (II) bis(trifluoromethanesulfonyl)imide) containing electrolyte. The high solubility of the novel PYR14NO3 salt in PYR14TFSI (>0.1 M) in comparison with other oxygenated precursors such as oxygen gas, NaNO3 or KNO3 (i.e. 10–15 mM) allows the formulation of a broad variety of electrolytes which opens wide possibilities to tune the physico-chemical properties of NiO films (e.g. morphology: from flat to nanostructured films). Furthermore, electrochemical deposition in an electrolyte containing low water concentration (>30 ppm by Karl Fisher titration) served to demonstrate that only a small amount of moisture dramatically affects the electrochemical reduction of NO3−, resulting in OH− generation close to the cathode and subsequent NiO(OH)/Ni(OH)2 deposition, as proved by X-ray diffraction and X-ray photoelectron spectroscopy. This finding highlights the importance of aprotic ionic liquids in developing a general electrochemical route for metal oxide deposition without the formation of metal hydroxide species, thus avoiding the requirement for post-deposition annealing treatments. The versatility of the present deposition route as well as its impact in (opto)electronic devices was pointed out by the successful preparation of nanostructured n–p ZnO/NiO heterojunctions exhibiting rectifying current– voltage characteristics. Synthesis of 1,3-di(4-amino-1-pyridinium)propane ionic liquid functionalized graphene nanosheets and its application in direct electrochemistry of hemoglobin Electrochimica Acta, 95, 15 April 2013, 71-79 Rui Li, Changxian Liu, Ming Ma, Zhengguo Wang, Guoqing Zhan, Buhai Li, Xian Wang, Huaifang Fang, Huijuan Zhang, Chunya Li 1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate (DAPPT) ionic liquid was successfully synthesized, and was used as a modifier to functionalize graphene nanosheets through covalent binding of amino groups and epoxy groups in an alkaline solution. The as-prepared graphene-DAPPT nanosheets (Gr-DAPPT) were confirmed with transmission electron microscopy (TEM), X___________________________________________________________________________ page 116 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/vis and FTIR spectroscopy. A biocompatible platform based on Gr-DAPPT was constructed for the immobilization of hemoglobin (Hb) through a cross-linking step with chitosan and glutaraldehyde. The direct electron transfer and bioelectrocatalytic reaction of Hb immobilized on Gr-DAPPT surface were achieved. A pair of reversible redox peaks of hemoglobin was observed, and bioelectrocatalytic activity toward the reduction of H2O2 was also demonstrated, displaying a potential application for the fabrication of novel biosensors to sense H2O2. Such results indicated that Gr-DAPPT based interface would be a promising platform for biomacromolecular immobilization and biosensor preparation. Investigation of Zr(IV) in LiF–CaF2: Stability with oxide ions and electroreduction pathway on inert and reactive electrodes Electrochimica Acta, 95, 15 April 2013, 185-191 M. Gibilaro, L. Massot, P. Chamelot, L. Cassayre, P. Taxil In this work, a detailed electrochemical study of the molten LiF–CaF2–ZrF4 system is provided in the 810–920 °C temperature range, allowing the determination of the reduction potential, the diffusion coefficient and the reduction mechanism of dissolved Zr(IV) on an inert Ta electrode. Addition of CaO in the molten salt is shown to cause Zr(IV) precipitation into an equimolar mixture of solid compounds, most likely ZrO2 and ZrO1.3F1.4. Underpotential deposition of Zr on Cu and Ni electrodes is also evidenced and Gibbs energy of formation of Cu–Zr compounds calculated by open circuit chronopotentiometry. Mixtures of unsaturated imidazolium based ionic liquid and organic carbonate as electrolyte for Li-ion batteries Electrochimica Acta, 95, 15 April 2013, 301-307 Maofeng Wang, Zhongqiang Shan, Jianhua Tian, Kai Yang, Xuesheng Liu, Haojie Liu, Kunlei Zhu Room temperature ionic liquid (RTIL) 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (AMIMTFSI) was obtained with high conductivity (7.8 mS/cm) and a wide electrochemical window (1–5.8 V). The AMIMTFSI based electrolytes with PC have been investigated by comparison with the ionic liquid 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (PMIMTFSI) based electrolytes. Raman observations revealed AMIMTFSI-based electrolytes achieved lower degree of [Li(TFSI)2]− anionic clusters and more free Li+ charge carriers than PMIMTFSIbased electrolyte. LiFePO4 cathode with AMIMTFSI-PC (50 wt%)–1 M LiTFSI electrolyte showed the best performance in the rate charge–discharge among the binary and ternary ionic liquid based electrolytes. The first reversible capacity of 159 mAh g−1 and coulombic efficiency of 97.2% at C/20 were obtained with AMIMTFSI-PC (50 wt%)–1 M LiTFSI electrolyte compared to 144.2 mAh g−1 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 117 PUBLICATIONS and 94.5% respectively with PMIMTFSI-PC (50 wt%)–1 M LiTFSI electrolyte. EIS results indicated that a stable protective layer was formed on the electrode surface in AMIMTFSI-based electrolyte. The layer helped to suppress the solvent decomposition and improve the cycling performance of Li-ion batteries. The Li/LiFePO4 cell showed interfacial stability and stable discharge capacities with a retention of 97.4% (151 mAh g−1) after 100 cycles at 0.1 C rate in AMIMTFSI-PC (50 wt%)–1 M LiTFSI electrolyte. Suppressed lithium dendrite growth in lithium batteries using ionic liquid electrolytes: Investigation by electrochemical impedance spectroscopy, scanning electron microscopy, and in situ 7Li nuclear magnetic resonance spectroscopy Journal of Power Sources, 228, 15 April 2013, 237-243 Nina Schweikert, Andreas Hofmann, Michael Schulz, Marco Scheuermann, Steven T. Boles, Thomas Hanemann, Horst Hahn, Sylvio Indris In this work, the formation of lithium dendrites in lithium/Li4Ti5O12 battery cells is studied using different experimental techniques. Electrochemical impedance spectroscopy is presented as a tool to investigate non-invasively the dendritic growth on a lithium metal surface in lithium/Li4Ti5O12 cells during numerous discharging/charging cycles. Scanning electron microscopy is used for visual inspection of the dendrite formation. In situ 7Li nuclear magnetic resonance spectroscopy is sensitive to quantitative changes at the lithium metal surface. Application to symmetrical lithium/lithium battery cells allows for a careful comparison of the investigated electrolytes. All these experimental methods provide consistent results. It is demonstrated that the growth of lithium dendrites is significantly correlated to the electrolyte employed. All electrolytes based on the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide (EMIM-TFSA) show reduced dendrite growth in comparison to the standard electrolyte for Li-ion batteries, lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC). LiPF6 in EMIMTFSA and LiPF6 in EMIM-TFSA/propylene carbonate suppress lithium dendrites most efficiently. Performance of an Electrochemical double layer capacitor based on coconut shell active material and ionic liquid as an electrolyte Journal of Power Sources, 228, 15 April 2013, 83-88 Maciej Galinski, Krzysztof Babeł, Krzysztof Jurewicz EDLCs based on the modified coconut shell raw material were manufactured with 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) as an electrolyte and a typical organic electrolyte based on acetonitrile. Three types of modification of the carbon material with different micro- to mesopore ratios were applied as the positive or negative electrode and tested. Obtained results showed different characteristic capacitances of 150–350 Fg−1, strongly ___________________________________________________________________________ page 118 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS dependent on the type of carbon material. Asymmetric EDLCs were manufactured from different carbon materials as positive and negative electrodes and a mass electrode fitting provided with an EDLC working at 3 V with a specific energy of 68.6 Wh kg−1 and power density of 36 W kg−1. Optimization of plastic crystal ionic liquid electrolyte for solid-state dyesensitized solar cell Electrochimica Acta, 94, 1 April 2013, 1-6 Junnian Chen, Tianyou Peng, Ke Fan, Renjie Li, Jiangbin Xia An efficient plastic crystal-based electrolyte is prepared by employing succinonitrile as solid solvent and binary ionic liquids as charge transfer mediators for dye-sensitized solar cells (DSSCs). It was found that combining succinonitrile with ionic liquids could improve the mechanical property of electrolyte and avoid the fluidity of ionic liquid, and the fabricated solid-state solar cell shows an overall conversion efficiency of 2.14%, which can be further improved to 5.50% after optimizing the addition amount of lithium perchlorate (LiClO4) as charge transfer promoter into the plastic crystal electrolyte, and the role of LiClO4 in the plastic crystal ionic liquid electrolyte is evaluated through electrochemical and photoelectrochemical measurements. The knowledge obtained from this plastic crystal-based electrolyte exhibits new eyeshot to find solid-state electrolyte for DSSCs with high performance. Heterogeneous electron-transfer rate constants for ferrocene and ferrocene carboxylic acid at boron-doped diamond electrodes in a room temperature ionic liquid Electrochimica Acta, 94, 1 April 2013, 49-56 Doo Young Kim, Ju Chan Yang, Hyoun Woo Kim, Greg M. Swain Heterogeneous electron-transfer rate constants were determined for ferrocene and ferrocene carboxylic acid (FCA) in the room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4), at borondoped microcrystalline diamond thin-film electrodes. Comparison data for FCA in 1 M KCl were also obtained. The apparent heterogeneous electron-transfer rate constant, , for FCA was 10× lower in the RTIL 1.5 (± 1.1) × 10−3 cm s−1 as compared to KCl 4.6 (± 1.3) × 10−2 cm s−1. The for ferrocene was also 10x lower in the RTIL 5.0 (± 1.2) × 10−3 cm s−1 as compared to a common organic electrolyte solution 5.5 (± 1.2) × 10−2 cm s−1. The diffusion coefficient for FCA (Dred) was determined by chronoamperometry to be 1.3 × 10−7 cm2 s−1, ca. 100× lower than the value (1.9 × 10−5 cm2 s−1) in KCl. The lower diffusion coefficient is consistent with the 100× greater viscosity of the RTIL. The lower values for these outer-sphere redox systems is attributed, at least in part, to a reduced number of attempts to surmount the activation barrier (i.e., a reduced nuclear frequency factor, νn) due to the more viscous medium. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 119 PUBLICATIONS Hierarchical LiMn2O4 microspheres for high rate lithium ion batteries, and direct electrochemistry and electrocatalysis Electrochimica Acta, 94, 1 April 2013, 165-171 Yuanxiang Gu, Zhanlei Tang, Ying Deng, Lei Wang Hierarchical LiMn2O4 microspheres were prepared using urchin-like α-MnO2 as a self-sacrificial template. As the cathode material for lithium ion batteries, the electrochemical properties were characterized by cyclic voltammetry and charge/discharge experiments. The results indicated that the LiMn2O4 microspheres had high discharge capacity and excellent cycle stability. Furthermore, a new electrochemical biosensor was constructed by immobilization of bovine myoglobin (Mb) and LiMn2O4 in a thin film of chitosan (CTS) on the surface of carbon ionic liquid electrode (CILE). Electrochemical behaviors of Mb entrapped in the film were investigated by cyclic voltammetry. A pair of well-defined redox peaks appears, which indicates a fast electron transfer rate of Mb with the underlying CILE. The electron transfer coefficient and electron transfer rate constant of Mb were calculated to be 0.47 and 1.04 s−1, respectively. The Mb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid (TCA) with a detection limit of 0.16 mmol L−1 (3σ). Ionic liquids based on bis(2,2,2-trifluoroethoxysulfonyl)imide with various oniums Electrochimica Acta, 94, 1 April 2013, 229-237 Shitao Fu, Shouzhe Gong, Chengyong Liu, Liping Zheng, Wenfang Feng, Jin Nie, Zhibin Zhou New class of hydrophobic ionic liquids based on bis(2,2,2trifluoroethoxysulfonyl)imide ([(CF3CH2OSO2)2N]−, TFESI−) anion with various oniums, including N,N-dialkylimidazolium, tetraalkyl (ether-containing alkyl) ammonium, N-alkyl-N-methyl-pyrrolidinium, and -piperidinium, are prepared and characterized. Their physicochemical and electrochemical properties, including phase transitions, thermal stability, viscosity, density, ionic conductivity and electrochemical windows, have been determined. The influences of the structural variations in both the cation and anion on the above properties are extensively discussed. The key features of these new TFESI−based ionic liquids are their low melting points (ranging from 9 to 44 °C) and/or low glass transition (between −74 and −61 °C), relatively low viscosities (44– 426 cP at 25 °C), good thermal stability (Td > 270 °C), and wide electrochemical windows (ranging from 5.7 to 6.4 V). Silver and silver–copper electrodeposition from a pyridinium-based ionic liquid ___________________________________________________________________________ page 120 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Electrochimica Acta, 94, 1 April 2013, 344-352 Juan M. Reyna-González, Juan C. Reyes-López, Martha Aguilar-Martínez Silver(I) was extracted from aqueous solutions in the absence and presence of copper(II) with the ionic liquid (IL) 3-butylpyridinium bis(trifluoromethanesulfonyl)imide, [3-BuPyr][NTf2]. After extraction, silver and silver–copper were electrodeposited on glassy carbon at room temperature from the ionic liquid phase. The mechanism of silver electrodeposition has been studied using electrochemical techniques such as cyclic voltammetry (CV) and chronoamperometry (CA). At suitably overpotentials silver electrocrystallization proceeds via a diffusion controlled mechanism and was analyzed using the Scharifker and Hills model for potentiostatic growth. The growth-nucleation mechanism of silver from the extracted phase is more progressive in character at low overpotentials, while at elevated overpotentials an instantaneous nucleation behavior was determined. In contrast, the silver nucleation closely followed the response predicted for instantaneous nucleation in neat [3-BuPyr][NTf2]. The electrochemical co-deposit of Ag–Cu was studied by linear sweep stripping voltammetry (LSSV). The resultant electrodeposits were characterized by scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis. Densities, excess molar and partial molar volumes for water + 1-butyl- or, 1-hexyl- or, 1-octyl-3-methylimidazolium halide room temperature ionic liquids at T = (298.15 and 308.15) K Journal of Molecular Liquids, 180, April 2013, 12-18 Nandhibatla V. Sastry, Nilesh M. Vaghela, Pradip M. Macwan Experimental densities for seven mixtures of water + 1-butyl-3methylimidazolium iodide, [C4mim][I], + 1-hexyl-3-methylimidazolium chloride, [C6mim][Cl], + 1-hexyl-3-methylimidazolium bromide, [C6mim][Br], + 1-hexyl-3-methylimidazolium iodide, + [C6mim][I], 1-octyl-3methylimidazolium chloride, [C8mim][Cl], + 1-octyl-3-methylimidazolium bromide, [C8mim][Br] and + 1-octyl-3-methylimidazolium iodide, [C8mim][I]) were measured across the composition at T = (298.15 and 308.15) K and atmospheric pressure. The excess molar volumes, VmE, were calculated and their compositional variation was mathematically represented by Redlich–Kister type equation. The partial excess molar volumes of water as well as the corresponding RTIL were calculated across the composition. The partial molar volumes at infinite dilution for the respective components and the corresponding standard transfer volumes for different combinations of water + RTIL mixtures were also calculated. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 121 PUBLICATIONS Characterization of caprolactam based eutectic ionic liquids and their application in SO2 absorption Journal of Molecular Liquids, 180, April 2013, 19-25 Baoyou Liu, Jingjing Zhao, Fuxiang Wei Five caprolactam (CPL) based eutectic ionic liquids (EILs) were prepared and their melting point, density, conductivity, viscosity, and decomposition temperature were detected. The EILs were investigated as potential absorbents for SO2 capture at 30 °C to 70 °C and 1 atmospheric pressure of pure gas. These properties of these EILs are similar to traditional ionic liquids and quite different from molecular solvents. In the tested temperature range, the density increases linearly with the increase of temperature, and the temperature dependence conductivity or viscosity is described by a VTF equation. CPL-imidazole (1:1) has the highest conductivity of 32.3 µs/cm at 30 °C and lowest viscosity of 48.6 mPa·s at 30 °C. The SO2 absorption capacities of CPL-organic amines based EILs are higher than CPL-organic acids based EILs. The solubility of SO2 in CPL-acetamide (1:1) is higher than BMImBF4 and lower than DMF. The solubility of SO2 in CPL-acetamide (1:1) is 0.497 g/g of mass fraction at 30 °C and the absorption is practically reversible. The absorption in CPL-acetamide (1:1) may probably follow a physical process by 1H NMR analysis. Room temperature ionic liquid-based dispersive liquid–liquid microextraction combined with flame atomic absorption spectrometry for the speciation of chromium(III) and chromium(VI) Journal of Molecular Liquids, 180, April 2013, 59-64 Shengping Wen, Jun Wu, Xiashi Zhu A simple method for the speciation of chromium(III)/chromium(VI) by flame atomic absorption spectrometry (FAAS) after room temperature ionic liquid (1octyl-3-methylimidazolium hexafluorophosophate, [C8MIM][PF6])-based dispersive liquid–liquid microextraction (DLLME) was developed. Chromium(VI) and total chromium (Cr(VI) and Cr(III)) could be extracted by [C8MIM][PF6] at the pH value of 5.0 and 6.5, respectively. The Cr(III) content was calculated by subtracting Cr(VI) from the total chromium. The main factors of DLLME were investigated. Under the optimized conditions, the detection limits (3σ) for Cr(III) and Cr(VI) were 1.00 µg L− 1 and 0.41 µg L− 1. The relative standard deviations (RSDs) for Cr(III) and Cr(VI) were 3.3% and 4.0% (n = 5, c = 80.00 µg L− 1), respectively. The calibration curve exhibited linearity over the concentration range of 5.00–200 µg L− 1 and 3.00–800 µg L− 1 for Cr(III) and Cr(VI). The proposed method was validated by the speciation of Cr(III)/Cr(VI) in certified reference materials for environmental water sample and real samples with satisfactory results. ___________________________________________________________________________ page 122 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ionic liquid functionalized nanoporous silica for removal of anionic dye Journal of Molecular Liquids, 180, April 2013, 95-100 Mansoureh Zarezadeh-Mehrizi, Alireza Badiei, Abdollah Rashidi Mehrabadi Nanoporous silica (NPS), with an average pore diameter of 2.4 nm and a surface area of 949 m2 g− 1, was synthesized by using nonyl phenol ethoxylated decylether (NP-10) and ethyl silicate 40% (ETS-40) under acidic condition. Ionic liquid functionalized adsorbent was prepared by grafting of N-methyl-N′propyltrimethoxysilylimidazolium chloride onto NPS for removal of methyl orange. The adsorbent was characterized by means of small-angle X-ray scattering, scanning electron microscopy, N2 adsorption–desorption isotherms, thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) and Raman spectroscopy. The kinetic data revealed that the adsorption process is consistent with the pseudo-second-order model. The Langmuir isotherm showed better correlation with the experimental data. The monolayer adsorption capacity of adsorbent was found to be 135 mg g− 1. Thermodynamic parameters such as enthalpy change (ΔH° = + 61.72 kJ mol− 1), free energy change (ΔG° < 0) and entropy change (ΔS° = + 222 J mol− 1 K− 1) indicate the endothermic and the spontaneous nature of the adsorption. Determination of the solubility parameter of ionic liquid 1-allyl-3methylimidazolium chloride by inverse gas chromatography Journal of Molecular Liquids, 180, April 2013, 135-138 Qiang Wang, Yali Chen, Lishuang Deng, Jun Tang, Zhengfang Zhang Some thermodynamic quantities were obtained for the interactions of ionic liquid 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), with n-hexane (n-C6), nheptane (n-C7), n-octane (n-C8), n-nonane (n-C9), chloroform, ethyl acetate, ether and acetone by the inverse gas chromatography (IGC) method in various temperatures. The thermodynamic parameters including the molar heat of sorption, weight fraction activity coefficient, Flory–Huggins interaction parameter and partial molar heat of mixing were calculated to judge the interactions between [AMIM]Cl and solvents at the studied temperatures. Also, the solubility parameter of [AMIM]Cl was found by plotting the graph of solubility parameters of probes. The results showed that the selected solvents nC6, n-C7, n-C8, n-C9, ethyl acetate, ether and acetone were poor solvents for [AMIM]Cl, while chloroform was a favorite solvent for [AMIM]Cl. The solubility parameter of [AMIM]Cl was calculated to be 23.33 (J·cm− 3)0.5 (343.15 K), 22.57 (J·cm− 3)0.5 (353.15 K), 21.63 (J·cm− 3)0.5 (363.15 K), and 20.88 (J·cm− 3)0.5 (373.15 K) by IGC. Glycerol based ionic liquid with a boron core: A new highly efficient and reusable promoting medium for the synthesis of quinazolinones Journal of Molecular Liquids, 180, April 2013, 139-144 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 123 PUBLICATIONS Hamid Reza Safaei, Mohsen Shekouhy, Vahid Shafiee, Mansooreh Davoodi A highly efficient and environmental benign procedure for the synthesis of 2,3dihydroquinazolin-4(1H)-ones via the condensation of carbonyl compounds with 2-aminobenzamide using a glycerol based ionic liquid with a boron core as a new and reusable promoting medium is described. A broad range of substrates including aldehydes and ketone were condensed with 2-aminobenzamide. All reactions are completed in short times and the products are obtained in good to excellent yields. The reaction medium could be recycled and reused several times without any loss of efficiency. Moreover, presented procedure has been applied successfully for the synthesis of some novel bis(pyrazolinone) derivatives. Co-solvent effects for aromatic extraction with ionic liquids Journal of Molecular Liquids, 180, April 2013, 145-153 C.V. Manohar, Tamal Banerjee, Kaustubha Mohanty This work tries to solve the current problems associated with ionic liquid (IL) mediated liquid–liquid extraction such as large viscosity and high cost. The performance of IL-solvent mixtures instead of pure ILs as extractant was systematically studied here. In this work we have separated benzene (aromatic component) from hexane (aliphatic component) by using the extractant ILAcetonitrile. The quaternary LLE experiments i.e., IL(1)-Acetonitrile(2)Benzene(3)-Hexane(4) was conducted at T = 298.15 K and 1 bar pressure. 1ethyl-3-methylimidazolium based ionic liquid coupled with the anions ethylsulphate [EtSO4] and Acetate [Ac] was used to separate benzene using the IL and acetonitrile as the solvent. It was found that for both the systems, the hexane composition in extract phase and the solvent composition in raffinate phase are nearly zero. This implies that a mixture of IL-Acetonitrile can be beneficial since it avoids cross-contamination which is usually a problem with conventional solvents. Although the selectivities are very high (~ 150), the capacities are low. With respect to selectivity values [EMIM][Ac] seems to be a more economical choice of solvent in terms of cross contamination. Both the NRTL and UNIQUAC models gave RMSD's less than unity. Determination and modeling of activity coefficients of the ionic liquid 1ethyl-3-methylimidazolium chloride in the (water + formamide) mixed solvent system at 298.2 K Journal of Molecular Liquids, 180, April 2013, 154-159 Bahram Ghalami-Choobar, Maryam Shekofteh-Gohari In this work, the results relating to the mean activity coefficient measurements for 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) in the (formamide + water) mixed solvent system using the potentiometric method have been reported. The electromotive force (emf) measurements were ___________________________________________________________________________ page 124 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS performed on the galvanic cell of the type: Ag|AgCl|[EMIm]Cl (m), formamide (wt.%), H2O (1 − wt) %|EMIm-ISE, in various mixed solvent systems containing 0, 10, 20, 30, and 40% mass fractions of formamide over ionic strength ranging from 0.0010 to 2.5000 mol·kg− 1 at T = 298.2 K. The modeling of this ternary system was made based on the Pitzer ion-interaction model. The values of the mean activity coefficients, the osmotic coefficients, the excess Gibbs free energy and the solvent activity together with Pitzer ion-interaction parameters (β(0), β(1) and ) for the series under investigated system were determined. Acidic ionic liquids catalyzed one-pot, pseudo five-component, and diastereoselective synthesis of highly functionalized piperidine derivatives Journal of Molecular Liquids, 180, April 2013, 187-191 Hamid Reza Shaterian, Kobra Azizi An efficient and one-pot quantitative procedure for the preparation of functionalized piperidine derivatives from pseudo five-component reactions of aromatic aldehydes, substituted anilines, and ethyl/methyl acetoacetate (molar ratio: 2/2/1) in the presence of acidic ionic liquids such as 1-methylimidazolium hydrogen sulfate ([Hmim]HSO4), 1,1,3,3-tetramethylguanidinium perchlorate ([TMG]ClO4), and 1,1,3,3-tetramethylguanidinium trifluoroacetate ([TMG]TFA) as the catalysts has been developed. The ionic liquids were stable during the reaction process and could also be reused several times without significant loss of their activities. Comparative study of interactions between thiophene\pyridine\benzene\heptane and 1-butyl-3-methylimidazolium trifluoromethanesulfonate by density functional theory Journal of Molecular Liquids, 180, April 2013, 207-214 Renqing Lü, Zhanqing Qu, Jin Lin Density functional theory has been employed to investigate the interactions between thiophene, pyridine, benzene, heptane and 1-butyl-3methylimidazolium trifluoromethanesulfonate ([BMIM][OTf]). The GGA/PW91 functionals and DNP basis set were used to optimize their geometries. The interactions between [BMIM][OTf] and thiophene, pyridine, benzene, and heptane have been ascribed to the formation of hydrogen bonds by NBO and AIM methods. The most stable gas-phase structure of [BMIM][OTf] ion pair indicates that hydrogen bonding interactions between the oxygen atoms on [OTf] anions and the C2-hydrogen on the imidazolium ring play a dominating role in the formation of the ion pair. Additional interactions are observed between [OTf] anion and the hydrogen atoms on the adjacent alkyl side chains of [BMIM] cation. The [OTf] anion tends to be located near a ring ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 125 PUBLICATIONS C2-proton, suggesting that the adsorption of thiophene, pyridine, benzene, and heptane on [BMIM][OTf] did not change the dominant interactions of [BMIM]– [OTf] pair. The predicted geometries, interaction energies and frontier orbitals implied the preferential adsorption of thiophene and pyridine on the [BMIM][OTf]. Mixtures of ionic liquid – Alkylcarbonates as electrolytes for safe lithiumion batteries Journal of Power Sources, 227, 1 April 2013, 8-14 Lucia Lombardo, Sergio Brutti, Maria Assunta Navarra, Stefania Panero, Priscilla Reale Mixtures of alkylcarbonate electrolytes with an ionic liquid (IL) and a lithium salt have been studied in order to develop new electrolytes for lithium-ion cells with enhanced safety profiles. In this work the influence of the addition of Nbutyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Py14TFSI) on the electrochemical properties of commercial carbonate-based electrolytes, i.e. 1 M LiPF6 in EC:DMC (LP30) and in EC:DMC:DEC (LP71) is reported. Four new electrolyte compositions have been prepared and characterized. The addition of the ionic liquid in the electrolyte carbonate-based solution results in (i) an ionic conductivity comparable with that of the pristine IL-free carbonate-based electrolyte, (ii) the enlargement of the electrochemical stability window, and (iii) a large reduction of the self-extinguish time (SET) of the electrolyte mixture when exposed to a free flame. All the newly developed electrolytes have been tested in lithium cells versus LiFePO4 and Li4Ti5O12 electrodes: the cells show good performances in galvanostatic cycling. The best performing electrolyte i.e. LP30/Py14TFSI 70/30 wt/wt has been also successfully tested in a full Li-ion cell realized by coupling LiFePO4 and Li4Ti5O12 electrodes. High-performance graphite negative electrode in a bis(fluorosulfonyl)imide-based ionic liquid Journal of Power Sources, 227, 1 April 2013, 60-64 Masaki Yamagata, Yukiko Matsui, Toshinori Sugimoto, Manabu Kikuta, Tetsuya Higashizaki, Michiyuki Kono, Masashi Ishikawa We evaluated the charge–discharge behavior of a graphite electrode in a 1-ethyl3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) ionic liquid. According to the charge–discharge tests, the graphite negative electrode exhibited a high rate of performance in LiTFSI/EMImFSI − (TFSI = bis(trifluoromethylsulfonyl)imide) in the voltage range of 0.005–1.5 V (vs. Li/Li+), and the performance was comparable to that in a conventional organic solution-based electrolyte, LiPF6/EC+DMC. Moreover, the addition of ___________________________________________________________________________ page 126 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS LiBOB (=lithium bis(oxalato)borate) improved the rate capability and lowtemperature operation of the graphite negative electrode, most likely owing to the low-resistivity solid electrolyte interface (SEI) derived from LiBOB. These results suggest that EMImFSI is a suitable electrolyte for lithium-ion batteries utilizing graphite negative electrodes and that optimization of the electrolyte composition with an additive can improve battery performance. Density, conductivity, viscosity, and excess properties of (pyrrolidinium nitrate-based Protic Ionic Liquid + propylene carbonate) binary mixture The Journal of Chemical Thermodynamics, 59, April 2013, 10-19 Julie Pires, Laure Timperman, Johan Jacquemin, Andrea Balducci, Mérièm Anouti Density, ρ, viscosity, η, and conductivity, σ, measurements of binary mixtures containing the pyrrolidinium nitrate Protic Ionic Liquid (PIL) and propylene carbonate (PC), are determined at the atmospheric pressure as a function of the temperature from (283.15 to 353.15) K and within the whole composition range. The temperature dependence of both the viscosity and conductivity of each mixture exhibits a non-Arrhenius behaviour, but is correctly fitted by using the Vogel–Tamman–Fulcher (VTF) equation. In each case, the best-fit parameters, such as the pseudo activation energy, and ideal glass transition temperature, T0 are then extracted. The excess molar volumes VE, and viscosity deviations from the ideality, Δη, of each investigated mixture were then deduced from the experimental results, as well as, their apparent molar volumes, Vϕ, thermal expansion coefficients αp, and excess Gibbs free energies (ΔG∗E) of activation of viscous flow. The VE, αpE, Δη values are negative over the whole composition range for each studied temperature therein. According to the Walden rule, the ionicity of each mixture was then evaluated as a function of the temperature from (283.15 to 353.15) K and of the composition. Results have been then discussed in terms of molecular interactions and molecular structures in this binary mixture. Solubilities of CO2, H2, N2 and O2 in ionic liquid 1-n-butyl-3methylimidazolium heptafluorobutyrate The Journal of Chemical Thermodynamics, 59, April 2013, 28-34 Lingyun Zhou, Jing Fan, Xiaomin Shang, Jianji Wang Ionic liquids (ILs) are promising in the capture and separation of CO2. In this work, IL 1-n-butyl-3-methylimidazolium heptafluorobutyrate, [C4mim][CF3CF2CF2COO], has been synthesized and characterized by 1H, 13C and 19F NMR spectra. Solubilities of CO2, H2, N2 and O2 in this IL have been determined at the temperature range from (303.15 to 333.15) K and the pressure up to 8.9 MPa. From these data, the Henry’s constant, the standard state solution Gibbs energy, standard state solution enthalpy and standard state solution ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 127 PUBLICATIONS entropy of these gases in [C4mim][CF3CF2CF2COO] were derived and analyzed from molecular interactions. It was shown that the solubility of CO2 is obviously higher than that in [C4mim][CF3COO] and [C4mim][CF3SO3] reported in literature, which makes this IL an attractive solvent for gas separation processes. Furthermore, these solubility data were well correlated by Pitzer model. Probing the self-aggregation of ionic liquids in aqueous solutions using density and speed of sound data The Journal of Chemical Thermodynamics, 59, April 2013, 43-48 M. Tariq, F. Moscoso, F.J. Deive, A. Rodriguez, M.A. Sanromán, J.M.S.S. Esperança, J.N. Canongia Lopes, L.P.N. Rebelo The aggregation behavior of three 1-alkyl-3-methylimidazolium chloride ionic liquids, [CnC1im]Cl (with n = 8, 10, 12), was probed at atmospheric pressure using density and speed of sound measurements in the 283.15 > T/K > 313.15 temperature range in aqueous solutions with mole fraction ranges of 0 > x([C8C1im]Cl) > 58 · 10−4, 0 > x([C10C1im]Cl) > 20 · 10−4, and −4 0 > x([C12C1im]Cl) > 4.8 · 10 . The results were used to calculate partial molar volumetric data and the isentropic compressibility of the solutions, both of which can be used as relevant properties to probe aggregate formation. In this context, micelle formation, solvation phenomena and water structural changes within the solutions are discussed in terms of the temperature and concentration dependence of the calculated properties. Solubility of carbon dioxide, nitrous oxide, ethane, and nitrogen in 1-butyl1-methylpyrrolidinium and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate (eFAP) ionic liquids The Journal of Chemical Thermodynamics, 59, April 2013, 65-71 S. Stevanovic, M.F. Costa Gomes The density and viscosity of the ionic liquids 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate [C1C4Pyrro][eFAP] and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate [P66614][eFAP] were measured as a function of temperature and pressure and as a function of temperature, respectively. These two ionic liquids are more viscous than those based in the same anion associated to imidazolium cations. The effect of the addition of water on the density and viscosity of [P66614][eFAP] was studied at pressures close to atmospheric and as a function of the temperature. This ionic liquid is only partially miscible with water, its solubility being of around in the range of (303 to 315) K. Experimental values of the solubility of carbon dioxide, nitrous oxide, ethane, and nitrogen were obtained as a function of temperature and at pressures close to atmospheric. Carbon dioxide and nitrous oxide are the more soluble gases with mole fraction solubilities up to 7 · 10−2. ___________________________________________________________________________ page 128 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ethane is four times and 1.3 times less soluble than carbon dioxide in [C1C4Pyrro][eFAP] and [P66614][eFAP], respectively. Nitrogen is one order of magnitude less soluble than the others gases in the two ionic liquids studied. In order to understand behavior of the different gases with these ionic liquids, the thermodynamic functions of solvation such as enthalpy and entropy were calculated from the variation of the Henry’s law constant with temperature. It is shown that the more favorable interactions of the gases with the ionic liquid explain the larger solubility of carbon dioxide and nitrous oxide in [C1C4Pyrro][eFAP]. In the case of [P66614][eFAP], it is the less favorable entropic contribution that explains the lower solubility of ethane in this ionic liquid. Determination of thermodynamic properties of the ternary electrolyte system {CoCl2 + Co(NO3)2 + H2O} by the potentiometric method at T = 298.15 The Journal of Chemical Thermodynamics, 59, April 2013, 114-120 Golam R. Vaghar, Mohammad A. Bagherinia, Azin Azarinezhadian In this work, the Pitzer ion interaction model and Harned rule were used to illustrate the ternary electrolyte system {CoCl2 + Co(NO3)2 + H2O}. The activity coefficients were determined using a potentiometric method. The galvanic cell used had no liquid junction of type: Co2+-ISE|CoCl2 (mA), Co(NO3)2 (mB), H2O|Ag.AgCl. The measurements were performed at T = 298.15 K and at total ionic strengths from 0.001 to 6.000 mol · kg−1 for different series of salt ratios r = = 1.00, 2.50, 5.00, 7.50, 10.00 and 15.00. The PVC based cobalt ionselective electrode (Co2+-ISE), the PVC based nitrate ion-selective electrode (NO3−-ISE) and the Ag/AgCl electrode used in this work were prepared in our laboratory and showed a reasonably good Nernst response. The experimental results showed that both Pitzer model and Harned rule were suitable to be used satisfactorily to describe this ternary system. Solubility measurements of hydrogen in 1-butyl-3-methylimidazolium tetrafluoroborate and the effect of carbon dioxide and a selected catalyst on the hydrogen solubility in the ionic liquid The Journal of Chemical Thermodynamics, 59, April 2013, 239-242 V.A. Toussaint, E. Kühne, A. Shariati, C.J. Peters The high pressure phase behavior of a binary mixture containing hydrogen (H2) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) is studied by measuring bubble-point pressures at different temperatures for three compositions with hydrogen mole fractions of 5, 7.5 and 10 mol%. Since this work is part of a study to design a hydrogenation process, using [bmim][BF4] as the reaction medium, the effects of adding carbon dioxide (CO2) or the ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 129 PUBLICATIONS hydrogenation catalyst (−)-1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene (cyclooctadiene)rhodium(I) tetrafluoroborate (Rh-MeDuPHOS) on H2 solubility in [bmim][BF4] was measured as well. All measurements were conducted in an autoclave set-up, allowing pressures up to 60 MPa and temperatures ranging from 313.15 up to 368.15 K. Results indicated that the presence of catalyst increased the H2 solubility in [bmim][BF4] compared to those of binary mixtures of H2 + [bmim][BF4] throughout the whole temperature range studied. However, the addition of CO2 to the binary system of H2 + [bmim][BF4] increases the H2 solubility at lower temperatures (<330 K), and decreases it at higher temperatures (>340 K) Ultrasonic velocity for an equimolar mixture of molten AgI and NaCl in the biphasic region The Journal of Chemical Thermodynamics, 59, April 2013, 250-253 Victor P. Stepanov, Vladimir I. Minchenko The ultrasonic velocities of a molten stratifying mixture composed of 0.5 AgI and 0.5 NaCl (the composition corresponding to the top of the miscibility gap) were measured along the saturation line for a wide temperature range via the pulse method to establish the characteristics of mixing salts with different chemical bonds. We show that the difference, Δu, between the magnitudes of the sound velocities for the coexisting phases decreases with increasing temperature and becomes zero at 1064 K. This temperature corresponds to the critical phase transition point, Tc. The temperature dependence of the sound velocity difference, Δu, is described by the equation Δu ≈ (Tc − T)Θ, where Θ = 0.896, which is less than that found for alkali halide melts (Θ = 1.02), in which longrange Coulomb forces between ions prevail. The results are discussed in terms of the peculiarity of the chemical bond in silver iodide. Convective mass transport in ionic liquids studied by electrochemical and electrohydrodynamic impedance spectroscopy Electrochimica Acta, 93, 30 March 2013, 32-43 Roberto M. Torresi, Lucas Lodovico, Tânia M. Benedetti, Maria R. Alcântara, Catherine Debiemme-Chouvy, Claude Deslouis In this work, the role of convective mass transport in two ionic liquids (ILs) that differ by the anions 1-butyl-2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide ([BMMI][Tf2N]) and 1-butyl-2,3-dimethylimidazolium tetrafluorborate ([BMMI][BF4]) were studied in the presence of ferrocene (Fc) as a redox tracer. A rotating disk electrode (RDE) system was used, and the use of electrochemical (EIS) and electrohydrodynamic (EHD) impedance spectroscopies allowed for a deeper analysis of mass transport and charge transfer at the surface of the electrode. The two ILs showed a ___________________________________________________________________________ page 130 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS viscoelastic character that was observed using a parallel plate geometry viscometer with a high storage-to-loss modulus ratio in a frequency domain where the RDE response was characterized by significant elongational flow kinematics. As a general conclusion, the observed effects were interpreted as unbalanced contributions of the elongational flow close to the electrode surface, which induced an anisotropic diffusivity that increased along the flow lines, and the effect of Fc and Fc+ as structure breakers or strengtheners in the diffusion layer. Finally, from EIS analysis, it was established that increasing the overpotential in the anodic direction yielded an increased Schmidt number, which indicated a detrimental effect on the mass transport of Fc+, whose production rate was also increased under the same conditions. EIS showed that the anion had an effect on the reaction rate of Fc oxidation and on the doublelayer capacitance value. Production of Fe–Ti alloy from mixed ilmenite and titanium dioxide by direct electrochemical reduction in molten calcium chloride Electrochimica Acta, 93, 30 March 2013, 143-151 Mrutyunjay Panigrahi, Etsuro Shibata, Atsushi Iizuka, Takashi Nakamura It is important to develop technologies for the production of high-purity metals and alloys for industrial applications. With the aim of addressing the urgent problem of depletion of resources and the commercial challenges associated with the development of new technologies, detailed research on the electrolysis of mixed FeTiO3/TiO2 in a molten CaCl2 electrolyte was conducted to prepare a high-purity, and high-opacity ferrotitanium (Fe–Ti) intermetallic alloy. Mixed solid oxides of FeTiO3 and TiO2 with FeTiO3:TiO2 molar ratios of 2.78:1.00 and 0.58:1.00 were used for the preparation of Fe–Ti intermetallic alloys (required molar ratios: Ti:Fe = 1.36:1.00 and 2.72:1.00). A mixed solid oxide of FeTiO3 and TiO2 was reduced electrochemically in a molten CaCl2 electrolyte at 950 °C and a constant voltage of 3.0 V. The metallic samples formed by the electrochemical reduction were analyzed using X-ray diffraction, scanning electron microscopy/energy-dispersive X-ray spectroscopy, electron-probe microanalysis, inductively coupled plasma atomic-emission spectroscopy, ion chromatography, and oxygen and carbon analyzers. The mixed oxide pellets were strongly and successfully reduced to a high-purity Fe–Ti intermetallic alloy of β-Ti (FeTi4) and FeTi phases of high-opacity and with small amounts of detected impurities. Electrochemistry of soluble UO22+ from the direct dissolution of UO2CO3 in acidic ionic liquid containing water Electrochimica Acta, 93, 30 March 2013, 264-271 Wendy J. Pemberton, Janelle E. Droessler, John M. Kinyanjui, Kenneth R. Czerwinski, David W. Hatchett ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 131 PUBLICATIONS The direct dissolution of UO2CO3 in neat and “wet” ionic liquid (IL) trimethyl-nbutylammonium bis(trifluoromethansulfonyl)imide [Me3NnBu][TFSI] is examined. The ionic liquid serves as both the solvent for the direct dissolution of UO2CO3(s) and the electrolyte solution for the electrochemical analysis of the soluble uranyl species. The solubility data indicate that displacement of the CO32− occurs slowly due to the low concentration of protons available from residual water in the pristine IL. Enhanced dissolution of UO2CO3 through the formation of carbonic acid H2CO3 is achieved after the addition of acid, bis(trifluoromethanesulfonyl)amide (HTFSI) and water. The soluble uranyl cation can then coordinate with the TFSI anion in place of the displaced CO32− anion following the decomposition of carbonic acid and purging of CO2(g) and water from the IL. The solubility of UO2CO3 was examined using liquid scintillation counting of 233U for the pristine ionic liquid. The “wet” ionic liquid containing HTFSI and soluble UO2CO3 was evaluated using UV/vis spectroscopy before and after dissolution. The electrochemical deposition of uranium species from ionic liquid was evaluated using cyclic voltammetry. The potential mediated deposition of uranium species was achieved and verified using scanning electron microscopy (SEM) and the solid uranium deposits were evaluated using energy dispersive X-ray emission spectroscopy (EDX). A new polymer electrolyte based on a discotic liquid crystal triblock copolymer Electrochimica Acta, 93, 30 March 2013, 279-286 Zlatka Stoeva, Zhibao Lu, Malcolm D. Ingram, Corrie T. Imrie A discotic liquid crystal triblock copolymer consisting of a central main chain triphenylene-based liquid crystal block capped at both ends by blocks of poly(ethylene oxide) (PEO) (MW = 2000 g mol−1) has been doped with lithium perchlorate in an EO:Li 6:1 ratio. The polymer electrolyte exhibits a phase separated morphology consisting of a columnar hexagonal liquid crystal phase and PEO-rich regions. The polymer electrolyte forms self-supporting, solid-like films. The ionic conductivity on initial heating of the sample is very low below ca. 60 °C but increases rapidly above this temperature. This is attributed to the melting of crystalline PEO-rich regions. Crystallisation is suppressed on cooling, and subsequent heating cycles exhibit higher conductivities but still less than those measured for the corresponding lithium perchlorate complex in poly(ethylene glycol) (MW = 2000 g mol−1). Instead the triblock copolymer mimics the behaviour of high molecular weight poly(ethylene oxide) (MW = 300,000 g mol−1). This is attributed, in part, to the anchoring of the short PEG chains to the liquid crystal block which prevents their diffusion through the sample. Temperature and pressure variations in ion mobility indicate that the ion transport mechanism in the new material is closely related to that in the ___________________________________________________________________________ page 132 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS conventional PEO-based electrolyte, opening up the possibility of engineering enhanced conductivities in future. Properties and application of ether-functionalized trialkylimidazolium ionic liquid electrolytes for lithium battery Journal of Power Sources, 226, 15 March 2013, 210-218 Yide Jin, Shaohua Fang, Ming Chai, Li Yang, Kazuhiro Tachibana, Shin-ichi Hirano Six low-viscosity ionic liquids based on trialkylimidazolium cation with one or two ether groups and TFSA− anion are used as new electrolytes for lithium battery, and compared with three typical trialkylimidazolium ILs without ether group. It is found that ether group in trialkylimidazolium cation can have an obvious effect on properties of electrolyte and performances of lithium battery. Introducing of ether group into trialkylimidazolium cation can be benefit for lithium redox behavior on Ni electrode, and affect passivation layer between IL electrolyte and lithium metal. Li/LiFePO4 cells using these ether-functionalized IL electrolytes without additive have good battery performance, and IM(2o1)1(2o2)-TFSA electrolyte owns better rate property. Electrochemical formation of Nd–Ni alloys in molten NaCl–KCl–NdCl3 Electrochimica Acta, 92, 1 March 2013, 349-355 Kouji Yasuda, Seitaro Kobayashi, Toshiyuki Nohira, Rika Hagiwara The electrochemical formation of Nd–Ni alloys was investigated in a molten NaCl–KCl–NdCl3 (0.50 mol%) system at 973 K. The electrochemical formation of several Nd–Ni alloy phases was indicated by cyclic voltammetry and opencircuit potentiometry. Alloy samples were prepared by one- or two-step potentiostatic electrolysis of a Ni plate electrode at various potentials. Scanning electron microscopy observations and X-ray diffraction measurements confirmed the formation of NdNi2, NdNi3, Nd2Ni7 and NdNi5. The formation reactions of the Nd–Ni alloys and the corresponding equilibrium potentials were determined. Supercapacitors based on graphene–polyaniline derivative nanocomposite electrode materials Electrochimica Acta, 92, 1 March 2013, 376-382 Punya A. Basnayaka, Manoj K. Ram, Elias K. Stefanakos, Ashok Kumar This manuscript discusses a comparative study of nanocomposite materials based on graphene and derivatives of PANI, i.e. ‘methoxy’ (OCH3) aniline and ‘methyl’ (CH3) aniline with graphene (G) for supercapacitor applications. The G-polyaniline (PANI), G-poly (o-methoxy aniline) [poly (o-anisidine) (POA)] ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 133 PUBLICATIONS and G-poly (o-methyl aniline) [poly (o-toluidine) (POT)] were synthesized by a chemical oxidative polymerization method and characterized to understand the nanocomposite formation of the materials. The electrochemical properties of GPANI, G-POA, and G-POT nanocomposites based supercapacitors were investigated using cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) techniques in 2 M H2SO4 electrolyte. The specific capacitances (Cp) of supercapacitors based on G-PANI, G-POA, and G-POT in 2 M H2SO4 electrolyte were estimated to be 400, 380, and 425 F/g, respectively. However, POT nanocomposite with graphene exhibited better capacitance (425 F/g) than the G-polyaniline or the G-POA based electrode materials. The relaxation time constants of 0.6, 2.5, and 5 s for the G-POT, G-PANI, and G-POA nanocomposite-based supercapacitors were calculated from the EIS analysis and such time constants revealed a quicker delivery of the stored energy than the carbon–carbon based supercapacitors. The high specific capacitance and small relaxation time constants of the Gsubstituted polyaniline paved the way for the fabrication of safe and stable supercapacitors. Synthesis and electrochemical property of sulfone-functionalized imidazolium ionic liquid electrolytes Electrochimica Acta, 92, 1 March 2013, 392-396 Wei Weng, Zhengcheng Zhang, John A. Schlueter, Khalil Amine Sulfone-functionalized imidazolium ionic liquids were synthesized from direct nucleophilic substitution for the first time. Detailed NMR analysis of the products revealed the competition pathways of classic SN2 substitution and E2 elimination in the synthesis reaction. Impurities from E2 elimination can easily be overlooked during the conventional method of ionic liquid preparation via SN2 substitution. Initial electrochemical examination of the synthesized ionic liquids shows good compatibility with Li1.1(Ni1/3Co1/3Mn1/3)0.9O2 cathode material. Li+ conducting polymer electrolyte based on ionic liquid for lithium and lithium-ion batteries Electrochimica Acta, 92, 1 March 2013, 404-411 Andrzej Lewandowski, Agnieszka Swiderska-Mocek, Lukasz Waliszewski Polymer electrolyte (PE), based on PVdF-co-HFP polymer network and MePrPipNTf2 + LiNTf2 ionic liquid (MePrPip: N-methyl-N-propylpiperidinium cation, NTf2 is bis(trifluoromethanesulphonyl)imide anion) was prepared. PE contained small amounts of vinylene carbonate. The performance of metalliclithium and graphite (G) anodes working together with the electrolyte were tested with the use of: electrochemical impedance spectroscopy (EIS), ___________________________________________________________________________ page 134 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS galvanostatic charging/discharging and scanning electron microscopy (SEM). Specific conductance of the membrane was ca. 4 mS cm−1 at 25 °C with activation energy of 14.35 kJ mol−1. Scanning electron microscopy images showed that the charged/discharged graphite anodes differed in morphology from the pristine material. The surface of graphite flakes was covered with small crystals with a diameter of ca. 1 µm (the solid electrolyte interface, SEI). When the graphite anode was soaked with the 1 M LiPF6 solution in PC + DMC (propylene carbonate and dimethyl carbonate, respectively), before the G|PE|Li cell assembling, its reversible capacity was ca. 340 mAh g−1 (after the 50th cycle). Intermolecular dynamics of room temperature ionic liquids having imidazolium cations Journal of Molecular Liquids, 179, March 2013, 54-59 Heesun Jun, Yukio Ouchi, Doseok Kim Room temperature ionic liquids having 1-butyl-3-methylimidazolium ([BMIM]) cations and three different anions ([BMIM][PF6], [BMIM][BF4], [BMIM]Br) were studied by using Optical Heterodyne Detected-Optical Kerr Effect (OHDOKE) spectroscopy to find out the effect of the anion size on the intermolecular dynamics. Fourier transformation of the time-domain OHD-OKE signals yielded a broad band in the spectra below 150 cm− 1. The modes with frequencies around 15, 80 and 100 cm− 1 used to fit the spectra all shifted to higher frequencies with the decrease in the anion size due to changes in the intermolecular force and the reduced mass. Prediction of surface tension of ionic liquids by molecular approach Journal of Molecular Liquids, 179, March 2013, 78-87 Seyyed Alireza Mirkhani, Farhad Gharagheizi, Nasrin Farahani, Kaniki Tumba Originally, Quantitative Structure Property Relationship (QSPR) models for the surface tension of ionic liquids are developed based on molecular descriptors. A large data set of 930 experimental surface tension data points for 48 ionic liquids is applied to derive the model. Seven descriptors are selected by genetic function approximation to relate the surface tension of ionic liquids to their corresponding anions and cation structures. To capture the nonlinear nature of surface tension, a model based on Least-Squared Supported Vector Machine (LSSVM) is also developed. The derived models are authenticated with several statistical validation techniques. Some physico-chemical properties of ethanolamine ionic liquids: Behavior in different solvents Journal of Molecular Liquids, 179, March 2013, 98-103 Dušica Simijonović, Zorica D. Petrović, Vladimir P. Petrović ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 135 PUBLICATIONS The series of ethanolamine derived ionic liquids (ILs) 1–9, was synthesized, characterized by IR and 1H NMR spectroscopy and investigated by DFT study, to explore their properties in solvents with different dielectric constants. The investigation of the anion–cation and ion–solvent interactions of ILs in solvents with different polarity was performed. The obtained results showed that solvation has significant influence on anion–cation interaction. The binding energies of the anion–cation interaction obtained in different solvents showed that in polar solvents ILs exist as separated solvated ions, while in solvents with lower polarity as the contacted ion pair. Density functional studies showed that solvation energies decrease with the increase of solvent polarity. Proficient synthesis of quinoxaline and phthalazinetrione derivatives using [C8dabco]Br ionic liquid as catalyst in aqueous media Journal of Molecular Liquids, 179, March 2013, 104-109 Abhijeet Mulik, Dattatraya Chandam, Prasad Patil, Dayanand Patil, Suryabala Jagdale, Madhukar Deshmukh Relatively less toxic and biodegradable ionic liquid [C8dabco]Br has been successfully used for the synthesis of quinoxaline and phthalazinetrione derivatives in an aqueous media. Recyclability of catalyst, high yields, use of environmentally benign aqueous media as solvent, simple product isolation and high atom economy are the noteworthy aspects of the protocols. Molten salt method of preparation and cathodic studies on layered-cathode materials Li(Co0.7Ni0.3)O2 and Li(Ni0.7Co0.3)O2 for Li-ion batteries Journal of Power Sources, 225, 1 March 2013, 374-381 M.V. Reddy, Bui Dang Tung, Lu Yang, Nguyen Dang Quang Minh, K.P. Loh, B.V.R. Chowdari Layered compounds, Li(Co0.7Ni0.3)O2 (I) and Li(Ni0.7Co0.3)O2(II) were prepared by molten salt method in temperature ranging from 650 to 950 °C. The effect of morphology, crystal structure and electrochemical properties of materials were evaluated by X-Ray Diffraction (XRD), Scanning Electron Microscopy and Brunauer-Emmett-Teller surface area, cyclic voltammetry (CV) and galvanostatic cycling. XRD pattern shows a hexagonal type structure with lattice parameters of a∼2.828 Å, c∼14.096 Å for I and a∼2.851 Å, c∼14.121 Å for II prepared in oxygen flow. The surface area of the compounds, I and II are 1.74 and 0.75 m2 g-1 respectively. CV studies show a main anodic peak occur at ∼3.8–3.94 V vs. Li and a cathodic peak occur at ∼3.6–3.7 V vs. Li. Galvanostatic cycling studies are carried out at a current rate of 30 mA g−1 in the voltage range of 2.5–4.3 V, at room temperature. Li(Co0.7Ni0.3)O2 prepared at 750 °C in air show a reversible capacity of 145 mAh g−1 at the 1st discharge cycle and 13% capacity fading between 2 and 56 cycles, whereas ___________________________________________________________________________ page 136 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Li(Ni0.7Co0.3)O2 reheated in the presence of oxygen deliver a high and stable reversible capacity of 165 mAh g−1 at the end of 60th cycle. A new method for manufacturing graphene and electrochemical characteristic of graphene-supported Pt nanoparticles in methanol oxidation Journal of Power Sources, 225, 1 March 2013, 356-363 Karim Kakaei, Mohammad Zhiani We report a Pt/graphene catalyst for the methanol oxidation. Graphene is synthesized from graphite electrodes using ionic liquid-assisted electrochemical exfoliation. Graphene-supported Pt electrocatalyst is then reduced by sodium borohydride with ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) as a stabilizing agent to prepare highly dispersed Pt nanoparticles on carbon graphene to use as methanol oxidation in direct methanol fuel cell (DMFC) catalysts. X-ray diffractometer and scanning electron microscopy technique are used to investigate the crystallite size and the surface morphologies respectively. The electrochemical characteristics of the Pt/graphene and commercial Pt/C catalysts are investigated by cyclic voltammetry (CV) in nitrogen saturated sulfuric acid aqueous solutions and in mixed sulfuric acid and methanol aqueous solutions. The catalytic activities of the Pt/graphene and Pt/C electrodes for methanol oxidation is 1315 A g−1 Pt and 725 A g−1 Pt, which can be revealed the particular properties of the exfoliated graphene supports. Furthermore, Pt/graphene exhibited a better sensitivity, signal-to-noise ratio, and stability than commercial Pt/C. 1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide as a cosolvent in Li-ion batteries Journal of Power Sources, 225, 1 March 2013, 113-118 Ketack Kim, Young-Hyun Cho, Heon-Cheol Shin 1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide (EMP-TFSI) is an ionic liquid with a melting temperature of 85 °C. Although it is a solid salt, it shows good miscibility with carbonate solvents, which allows EMP-TFSI to be used as a co-solvent in these systems. Ethylene carbonate is another solid cosolvent used in Li-ion batteries. Due to its smaller cationic size, EMP-TFSI provides better conductivity as a co-solvent than 1-methyl-1-propyl piperidinium bis(trifluoromethanesulfonyl)imide (MPP-TFSI), which is the smallest room-temperature piperidinium liquid salt known. In cells with 50 wt% IL and 50 wt% carbonate electrolyte, an EMP-TFSI mixed electrolyte performs better than an MPP-TFSI mixed electrolyte. Additionally, the discharge capacity values obtained from rate capability tests carried out with mixed EMP-TFSI are as good as those conducted with a pure carbonate electrolyte. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 137 PUBLICATIONS Cycle versus voltage hold – Which is the better stability test for electrochemical double layer capacitors? Journal of Power Sources, 225, 1 March 2013, 84-88 D. Weingarth, A. Foelske-Schmitz, R. Kötz The stability of electrochemical double layer capacitors (EDLC) utilizing an ionic liquid and tetraethylammoninium tetrafluoroborate (TEABF4) in acetonitrile electrolyte was tested by cycling and by constant voltage hold tests. It turned out that possible degradation of the EDLC is visible in the voltage hold test after a time period which is typically much shorter if compared to the cycle tests. A constant capacitance during several thousands of cycles does not necessarily indicate stability. For capacitor cells using a carbon black as active material and an ionic liquid as electrolyte constant capacitance could be demonstrated over 12,000 cycles between 0 V and 3.75 V. Clear ageing was observed, however, during the voltage hold test at 3.75 V after 300 h. For a maximum voltage of 3.5 V both the cycle and the voltage hold test indicated stable performance over 12,000 cycles or 500 h, respectively. For capacitors using an activated carbon as active material and standard electrolyte TEABF4 in acetonitrile both tests clearly demonstrated degradation for a maximum cell voltage of 3.5 V. The evolution of capacitance loss observed for the voltage hold test at 3.25 V is in good agreement with the degradation observed at 3.5 V for the voltage hold test. Physicochemical properties and activity coefficients at infinite dilution for organic solutes and water in a novel bicyclic guanidinium superbasederived protic ionic liquid The Journal of Chemical Thermodynamics, 58, March 2013, 62-69 Urszula Domańska, Marek Królikowski, William E. Acree Jr., Gary A. Baker The activity coefficient at infinite dilution, , was determined by gas–liquid chromatography at temperatures from T = 308.15 to T = 348.15 K for 54 assorted solutes—among them, alkanes (linear, branched, or cyclic), alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, tetrahydrofuran, 1,4-dioxane, ethers, acetone, ketones, acetonitrile, pyridine, and 1nitropropane—in the novel bicyclic guanidine superbase-derived protic ionic liquid 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine bis(pentafluoroethyl)sulfonylimide, [MTBDH][BETI]. The partial molar excess Gibbs free energy , the partial molar excess enthalpy , and entropy at reference temperature at infinite dilution were calculated from the experimental values obtained over this temperature range. The gas–liquid partition coefficient, , was calculated for each solute and discussed in light of the Abraham solvation parameter model. The density of the IL as a function of temperature was also measured. The selectivities for heptane/benzene, heptane/thiophene, heptane/pyridine, and heptane/nitropropane separation problems were calculated ___________________________________________________________________________ page 138 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS from and compared to literature values for select ILs, as these separation problems are central to the petroleum industry. Thermodynamic investigation of the LiF–ThF4 system The Journal of Chemical Thermodynamics, 58, March 2013, 110-116 E. Capelli, O. Beneš, M. Beilmann, R.J.M. Konings A thermodynamic investigation of the LiF–ThF4 system is presented in this study. The enthalpy of mixing of the (Li,Th)Fx liquid solution was measured for the first time using a method designed for conventional DSC technique. To verify the possibility to measure the mixing enthalpy with the used calorimeter, the known LiF–KF system was first investigated and compared to the literature data. After the successful test, this technique was applied to investigate the LiF– ThF4 system and obtained novel results are presented in this study. Furthermore, using the DSC technique, new equilibrium data of the LiF–ThF4 phase diagram were measured, confirming the stability of the LiThF5 phase. The intermediate compound Li3ThF7 was synthesized and its enthalpy of fusion was determined. Considering the new experimental data, the LiF–ThF4 system was re-optimized using a quasi chemical model for the description of excess Gibbs parameters of the liquid solution. Influence of anion on thermophysical properties of ionic liquids with polar solvent The Journal of Chemical Thermodynamics, 58, March 2013, 269-278 Varadhi Govinda, P. Madhusudhana Reddy, Pankaj Attri, P. Venkatesu, P. Venkateswarlu In this work, we have reported a series of ionic liquids (ILs) involving a common cation trimethyl ammonium, ([(CH3)3NH]+), with generally used anions (acetate, [CH3COO]−, sulfate, [HSO4]−, phosphate, [H2PO4]−). To address the molecular interactions between the relatively new class of solvents such as trimethylammonium acetate [(CH3)3NH+] [CH3COO–] (TMAA), + − trimethylammonium hydrogen sulfate [(CH3)3NH ][HSO4 ] (TMAS), and trimethylammonium dihydrogen phosphate [(CH3)3NH+][H2PO4–] (TMAP), with the polar solvent, dimethylsulfoxide (DMSO), the density (ρ), speed of sound (u) and viscosity (η) values have been measured over complete concentration range and wide temperature range from 298.15 K to 313.15 K in steps of 5 K under ambient pressure. By using these experimental results, excess volumes (VE), isentropic compressibility deviations (Δκs) and viscosity deviations (Δη) were obtained for all these binary systems at all experimental temperatures. The results are correlated by the Redlich−Kister type function to derive the coefficients and estimate the standard error. Further, the results for observed anion dependent phenomena and temperature influence on measured and derived properties are also discussed. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 139 PUBLICATIONS Activity coefficients at infinite dilution of organic solutes in the ionic liquid PEG-5 cocomonium methylsulfate at T = (313.15, 323.15, 333.15, and 343.15) K: Experimental results and COSMO-RS predictions The Journal of Chemical Thermodynamics, 58, March 2013, 322-329 Prashant Reddy, M. Aslam Siddiqi, Burak Atakan, Michael Diedenhofen, Deresh Ramjugernath Activity coefficients at infinite dilution have been determined for 25 polar and non-polar organic solutes (alkanes, cycloalkanes, alk-1-enes, alk-1-ynes, aromatic compounds, alcohols, and ketones) in the ionic liquid PEG-5 cocomonium methylsulfate with gas–liquid chromatography at four different temperatures, T = (313.15, 323.15, 333.15, and 343.15) K. Packed columns with phase loadings of 0.28 and 0.34 ionic liquid mass fraction in the stationary phase were employed to obtain values at each temperature investigated. Speed of sound, density, and refractive index values have also been measured for the pure ionic liquid at P = 0.1 MPa and T = (303.15, 313.15, 323.15, 333.15, and 343.15) K. The uncertainties in the sound speeds, densities, and refractive indices are estimated to be values of 0.9 m · s−1, 0.00003 g · cm−3, and 0.00002, respectively. Partial molar excess enthalpies at infinite dilution were calculated for the solutes from the temperature dependency of the values for the temperature range of this study. The uncertainties in the determinations of and values are 5% and 10%, respectively. Selectivity values at infinite dilution for hexane/benzene, cyclohexane/benzene, hexane/hex-1-ene, and hexane/ethanol separations have been calculated. These have been compared against values obtained from COSMO-RS predictions. Influence of the pressure, temperature, cation and anion on the volumetric properties of ionic liquids: New experimental values for two salts The Journal of Chemical Thermodynamics, 58, March 2013, 440-448 Teresa Regueira, Luis Lugo, Josefa Fernández Experimental densities of two ionic liquids (ILs), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4C1Pyrr][NTf2]) and 1-(2-methoxyethyl)-1methyl-pyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([C1OC2C1Pyrr] [(C2F5)3PF3]), were measured over a broad temperature and pressure range, i.e. from (278.15 to 398.15) K and up to 120 MPa, respectively. The isobaric thermal expansion coefficient of the two ILs was determined from these measurements finding a non-monotonous behaviour over the entire pressure range. The density values obtained were used to analyse the prediction ability of the methods proposed by Gardas and Coutinho and by Jacquemin et al. Furthermore, the influence of the cation and anion structure on the densities and the isothermal compressibilities was analyzed, also considering literature values. ___________________________________________________________________________ page 140 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Properties of pure n-butylammonium nitrate ionic liquid and its binary mixtures of with alcohols at T = (293.15 to 313.15) K The Journal of Chemical Thermodynamics, 58, March 2013, 449-459 Yingjie Xu, Bin Chen, Wu Qian, Haoran Li Values of the density and viscosity of the pure ionic liquid n-butylammonium nitrate (N4NO3) and its binary mixtures with methanol, ethanol, 1-propanol, and 1-butanol were measured at temperature ranging from T = (293.15 to 313.15) K. The thermal expansion coefficient, molecular volume, standard entropy, and lattice energy of N4NO3 were deduced from the experimental density results. The temperature dependence of the viscosity of N4NO3 was fitted to the fluidity equation. Excess molar volumes VE and viscosity deviations Δη for the binary mixtures were calculated and fitted to the Redlich–Kister equation with satisfactory results. Both excess molar volumes and viscosity deviations show negative deviations for (N4NO3 + alcohol) mixtures. The effect of the temperature and the size of the alcohol on the excess molar volumes and viscosity deviations are discussed and analysed. Other derived properties, such as the apparent molar volume, partial molar volume, excess partial molar volume, thermal expansion coefficient, and excess thermal expansion coefficient of the above-mentioned systems were also calculated. High-safety lithium-sulfur battery with prelithiated Si/C anode and ionic liquid electrolyte Electrochimica Acta, 91, 28 February 2013, 58-61 Yang Yan, Ya-Xia Yin, Sen Xin, Jing Su, Yu-Guo Guo, Li-Jun Wan A Li-S battery with safety configuration has been constructed by employing electrochemically prelithiated Si/C microspheres as an anode, S/C composites as a cathode, and a room temperature ionic liquid of n-Methyl-n-Allylpyrrolidinium bis(trifluoromethanesulfonyl)imide (RTIL P1A3TFSI) as an electrolyte. Galvanostatic discharge–charge tests show that the as-assembled Li-S battery could deliver a high discharge specific capacity of 1457 mA h g−1 (based on the sulfur cathode) at 0.1 C, indicating the high Li electroactivity of the system. The reversible capacity is 926.4 mA h g−1 in the first cycle, and could remain as high as 670 mA h g−1 after 50 cycles, revealing the favorable compatibility between the RTIL P1A3TFSI electrolyte and the two electrode materials in the Li-S battery. The as-assembled Li-S battery in the charged state can be used for energy output without activation process by charging. This green rechargeable Li-S battery typically gives an output voltage of 1.5 V per cell, which raises the potential for directly replacing the widely used 1.5 V primary alkaline batteries and dry cells without any change of external circuits of current electronic devices but more rechargeable and powerful. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 141 PUBLICATIONS Physicochemical properties of N-methoxyethyl-N-methylpyrrolidinum ionic liquids with perfluorinated anions Electrochimica Acta, 91, 28 February 2013, 101-107 Jakub Reiter, Elie Paillard, Lorenzo Grande, Martin Winter, Stefano Passerini Four room-temperature ionic liquids (RTILs) based on N-methyl-Nmethoxyethylpyrrolidinium (PYR12O1+) and fluorinated sulfonylimides, bis(fluorosulfonyl)imide (FSI−), bis(trifluoromethanesulfonyl)imide (TFSI−), bis(pentafluoroethylsulfonyl)imide (BETI−) and (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl)imide (IM14−) anion have been synthesised and intensively investigated from an electrochemical and physico-chemical point of view, including thermal behaviour, viscosity, conductivity and electrochemical stability. The prepared ionic liquids are thermally stable (over 200 °C in N2 and over 180 °C in O2 atmosphere) and electrochemically stable with electrochemical stability windows on platinum in the range from 4.7 V (PYR12O1FSI) to 5.4 V (PYR12O1IM14). Conductivity decreases in the series FSITFSI-BETI-IM14 according to the viscosity increase. DSC measurements showed no crystallisation down to −150 °C for PYR12O1TFSI and PYR12O1IM14. Electrochemical biosensor based on graphene, Mg2Al layered double hydroxide and hemoglobin composite Electrochimica Acta, 91, 28 February 2013, 130-136 Wei Sun, Yaqing Guo, Yaping Lu, Anhui Hu, Fan Shi, Tongtong Li, Zhenfan Sun A graphene (GR) and Mg2Al layered double hydroxide (LDH) composite was prepared and used for the immobilization of hemoglobin (Hb) on a carbon ionic liquid electrode (CILE) to obtain an electrochemical biosensor. Morphology of the materials was analyzed by scanning electron microscopy and transmission electron microscopy. Spectroscopic experiments were performed to characterize the conformational changes of Hb in the GR-LDH membrane. Electrochemical investigation showed a pair of well-defined quasi-reversible redox peaks appeared with redox peak potentials as −0.145 V (Epa) and −0.248 V (Epc) in phosphate buffer solution (0.1 mol L−1, pH 3.0) at the scan rate of 100 mV s−1, which indicated that direct electrochemistry of Hb was realized on the modified electrode. So the presence of GR-LDH composite could facilitate the electron transfer rate between CILE and the electroactive center of Hb. The immobilized Hb in GR-LDH modified electrode exhibited excellent electrocatalytic reduction to trichloroacetic acid in the concentration range from 1.6 to 25.0 mmol L−1 with the detection limit as 0.534 mmol L−1 by cyclic voltammetry, which indicated the successfully preparation of a third-generation electrochemical biosensor. Dye-sensitized solar cells based on agarose gel electrolytes using allylimidazolium iodides and environmentally benign solvents Electrochimica Acta, 91, 28 February 2013, 208-213 ___________________________________________________________________________ page 142 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Hsin-Ling Hsu, Cheng-Fang Tien, Ya-Ting Yang, Jihperng Leu Novel agarose gel electrolytes are prepared by allylimidazolium iodides-based ionic liquids and environmentally benign co-solvents (propylene carbonate (PC) and dimethyl sulfoxide (DMSO)) for dye-sensitized solar cells (DSSCs). Among 1-allyl-3-ethylimidadolium iodide (AEII), 1-allyl-3-propylimidazolium iodide (APII), 1-3-diallylimidazolium iodide (DAII), and 1-methyl-3propylimidazolium iodide (MPII) ionic liquids, the agarose gel electrolyte containing AEII exhibits the best DSSC performance. The efficiency of the DSSC using the agarose gel electrolyte containing 1.5 M AEII and 0.65 wt% agarose is 5.89% with the highest I3− diffusion coefficient of 7.7 × 10−6 cm2 s−1. The performance of the AEII ionic liquid-based agarose gel electrolyte is comparable to the liquid electrolyte based on 3-methoxypropionitrile (MPN) (5.84%) under illumination at AM 1.5, 100 mW cm−2. Moreover, the DSSC performance of the allylimidazolium iodides ionic liquid-based agarose electrolyte is determined by the interaction between ionic liquid and agarose, which affects the rigidity of the ion channels and the I3− diffusion coefficient. Ionogels based on ionic liquids as potential highly conductive solid state electrolytes Electrochimica Acta, 91, 28 February 2013, 219-226 S.A.M. Noor, P.M. Bayley, M. Forsyth, D.R. MacFarlane The preparation and properties of ionogels as potential highly conductive solid state electrolytes has been investigated. The ionogels have been prepared by a one-pot sol–gel synthesis using tetraethoxysilane (TEOS) in an ionic liquid, 1butyl-3-methyl imidazolium tetrafluoroborate [BMIm][BF4]. The effect of silica content in the ionogels was characterized and analyzed in terms of chemical interactions, thermal stability and ionic conductivity. Immobilization of the IL in the silica network was observed even at high loading of IL (97 wt.%). Hydrogen bond networks between BF4− and the hydroxyl group in the silica was suggested as the mechanism of this immobilization, which was characterized by FTIR and solid-state NMR. TGA analysis shows that the prepared ionogels were stable up to around 450 °C, where a-final one-step degradation occurs. The ionic conductivity was found to decrease as the amount of silica increased. However, with high loading of IL (97 wt.%) the ionic conductivity was close to that of the pure IL. From the results obtained, these ionogels can be considered potential candidates for electrochemical devices where high ionic conductivity in solid state materials is desirable. Thermodynamic properties of calcium–magnesium alloys determined by emf measurements Electrochimica Acta, 91, 28 February 2013, 293-301 Jocelyn M. Newhouse, Sophie Poizeau, Hojong Kim, Brian L. Spatocco, Donald R. Sadoway ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 143 PUBLICATIONS The thermodynamic properties of calcium–magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi)|CaF2|Ca(in Mg) cell over the temperature range 713–1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca–Mg alloys, calcium mole fractions varying from xCa = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs–Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 × 10−4 and 0.94 versus pure calcium. The molecular interaction model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca–Mg liquid alloys. Based on this work, Ca–Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte. Printable electrolytes for highly efficient quasi-solid-state dye-sensitized solar cells Electrochimica Acta, 91, 28 February 2013, 302-306 Chaolei Wang, Liang Wang, Yantao Shi, Hong Zhang, Tingli Ma Novel polymer gel electrolytes (PGEs) with high ionic conductivity based on polyvinyl (acetate-co-methyl methacrylate) [P(VA-co-MMA)] were prepared by soaking porous copolymers in an organic electrolyte solution [acetonitrile (ACN) or 3-Methoxypropionitrile (MPN)] that contained an I3−/I− as redox couple. Quasi-solid-state dye-sensitized solar cells (QS-DSSCs) were fabricated with the PGEs, and the best PGE was selected and optimized. Using the best PGE and under 100 mW cm−2 light illumination (AM1.5), the QS-DSSC achieved a high photovoltaic conversion efficiency of 9.10%, nearly the same as that for the DSSC based on the original liquid electrolyte. Introduction of TiO2 nanoparticles into the PGEs further enhanced PGEs ionic conductivity and the conversion efficiency to 9.40%. Subsequent results revealed that our QS-DSSC had a better stability because it could maintain 96.7% of its initial efficiency after long-time (1000 h) exposure to simulative sunlight. Besides, for the first time, large-area QS-DSSCs were fabricated by screen printing of PGE, other than the traditional vacuum injection that was infeasible for the viscous gel electrolyte. Finally, our 5 cm × 7 cm QS-DSSC sub-module exhibited a conversion efficiency higher than 4%. Hydrophobic ionic liquid immoblizing cholesterol oxidase on the electrodeposited Prussian blue on glassy carbon electrode for detection of cholesterol Electrochimica Acta, 90, 15 February 2013, 203-209 Xiuhui Liu, Zhihan Nan, Yu Qiu, Lichun Zheng, Xiaoquan Lu ___________________________________________________________________________ page 144 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A novel cholesterol biosensor was fabricated on hydrophobic ionic liquid (IL)/aqueous solution interface. The hydrophobic IL thin film played a signal amplification role because it not only enriched the cholesterol from the aqueous solution, but also immobilized matrix for cholesterol oxidase (ChOx). Prussian blue (PB) as advanced sensing materials was used as effective low-potential electron transfer mediation toward hydrogen peroxide (H2O2). The fabricated ILChOx/PB/Glassy carbon electrode (GCE) was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammogram (CV), respectively. And it exhibited a linear response to cholesterol in the range of 0.01–0.40 mM with a detection limit of 4.4 µM. In addition, the kinetics behavior of cholesterol at IL-Chox/PB/GCE electrode was examined, and the electrocatalytic mechanism was proposed as shown in first scheme. ChOx immobilized in hydrophobic IL thin film was used as the first electrocatalyst for the cholesterol into H2O2, and the PB film onto the GCE was used as the second electrocatalyst for the 2e− reduction of the produced H2O2 into H2O. Nanomolar simultaneous determination of levodopa and serotonin at a novel carbon ionic liquid electrode modified with Co(OH)2 nanoparticles and multi-walled carbon nanotubes Electrochimica Acta, 90, 15 February 2013, 317-325 Ali Babaei, Ali Reza Taheri, Majid Aminikhah A novel modified carbon ionic liquid electrode is prepared as an electrochemical sensor for simultaneous determination of levodopa (l-dopa) and serotonin (5HT). The experimental results suggest that a carbon ionic liquid electrode modified with multi-walled carbon nanotubes and cobalt hydroxide nanoparticles, and coated with Nafion (Nafion/Co(OH)2–MWCNTs/CILE), accelerates the electron transfer reactions of l-dopa and 5-HT. In addition it shows no significant interferences of uric acid and ascorbic acid as electroactive coexistent compounds with l-dopa and 5-HT in biological systems. The fabricated sensor revealed some advantages such as convenient preparation, good stability and high sensitivity toward 5-HT and l-dopa determination. The DPV data showed that the obtained anodic peak currents were linearly dependent on the l-dopa and 5-HT concentrations in the range of 0.25–225 and 0.05–75 µmol L−1, respectively. The applicability of the modified electrode was demonstrated by simultaneous determination of 5-HT and l-dopa in human serum. The influence of the electrochemical and thermal stability of mixtures of ionic liquid and organic carbonate on the performance of high power lithium-ion batteries Electrochimica Acta, 90, 15 February 2013, 641-648 S. Menne, R.-S. Kühnel, A. Balducci ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 145 PUBLICATIONS In this work we report on the use of 0.3 M LiTFSI in PC–PYR14TFSI (50:50 wt.%) as electrolyte in lithium-ion batteries (LIBs). Conductivity, viscosity and electrochemical stability of this electrolyte were investigated and compared with those of the electrolytes 1 M LiPF6 in PC and 0.3 M LiTFSI in PC. The thermal stability of these electrolytes at 60 °C was also investigated. LIBs containing LTO as anode and LFP as cathode were assembled and tested in the three electrolytes at room temperature and 60 °C. The results of these tests show that the use of 0.3 M LiTFSI in PC–PYR14TFSI (50:50 wt.%) allows the realization of LIBs able to deliver high capacity and to display high cycling stability at both temperatures. Lithium intercalation in nanostructured thin films of a mixed-valence layered vanadium oxide using an ionic liquid electrolyte Journal of Power Sources, 224, 15 February 2013, 72-79 Tânia M. Benedetti, Emily Redston, Willian G. Menezes, Dayane M. Reis, Jaísa F. Soares, Aldo J.G. Zarbin, Roberto M. Torresi Nanostructured thin films of a mixed-valence, layered vanadium oxide were prepared using layer-by-layer deposition. The thin films were characterized by electronic (UV–vis) spectroscopy, quartz crystal microbalance, profilometry and scanning electron microscopy techniques. The highest charge capacity was obtained for films that consisted of 25 bilayers. The electrochemical characterization of the films was performed in conventional organic solvent and ionic liquid (IL) based electrolytes. The results revealed better performance, in terms of stability during consecutive charge/discharge cycles, when ILs were employed. This can be attributed to several factors, including reduced mechanical stress caused by insertion of more than 1 mol of Li+ per mol of V5+ in the film structure, decrease of crystallinity in the electrode material during the first few charge/discharge cycles and/or formation of a more compatible SEI. Nanostructured thin films of layered vanadium oxide prepared using layer-bylayer deposition showed potential for applications in lithium microbatteries. Characterization of N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide-based polymer electrolytes for high safety lithium batteries Journal of Power Sources, 224, 15 February 2013, 93-98 Jae-Kwang Kim, Leszek Niedzicki, Johan Scheers, Cho-Rong Shin, Du-Hyun Lim, Wladyslaw Wieczorek, Patrik Johansson, Jou-Hyeon Ahn, Aleksandar Matic, Per Jacobsson Poly(vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP) membrane was prepared by electrospinning. The membranes served as host matrices for the preparation of ionic liquid-based polymer electrolytes (ILPEs) by activation with non-volatile, highly thermally stable, and safe room temperature ionic liquid ___________________________________________________________________________ page 146 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS (RTIL) electrolytes; N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py14TFSI) complexed with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). In this work, the first combination of electrospun PVdF-HFP fiber polymer host and pyrrolidinium-based ionic electrolyte was employed for highly stable lithium batteries. The ILPE exhibited low Li+–TFSI coordination, low crystallinity, high thermal stability, high electrochemical stability, and high ionic conductivity with a maximum of 1.1 × 10−4 S cm−1 at 0 °C. The ILPE exhibited good compatibility with a LiFePO4 electrode on storage and good charge–discharge performance in Li/ILPE/LiFePO4 cells at room temperature, delivering specific capacities of 143 and 115 mA h g−1 at 0.1 and 1 C-rates. The ILPE also exhibited stable cycle properties and have therefore been demonstrated to be suitable for lithium battery applications. Catalyst-free porous carbon cathode and ionic liquid for high efficiency, rechargeable Li/O2 battery Journal of Power Sources, 224, 15 February 2013, 115-119 Francesca Soavi, Simone Monaco, Marina Mastragostino Li/O2 batteries are a breakthrough in battery technology for powering long-range electric vehicles. The viability of high efficiency, rechargeable Li/O2 battery is demonstrated by the use of catalyst-free meso-macroporous carbon cathode and N-butyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid-based electrolyte. The carbon electrode, obtained by a simple, low-cost template method, features a high specific capacity of 2500 mAh g−1 at 2.6 V vs. Li+/Li and, more importantly, a recharge potential lower than 3.8 V vs Li+/Li that prevents secondary reactions in the ionic liquid detrimental for battery rechargeability and makes it possible to reach a recharge efficiency of 90%. Single-step in-situ preparation of thin film electrolyte for quasi-solid state quantum dot-sensitized solar cells Journal of Power Sources, 224, 15 February 2013, 152-157 Shen Wang, Quan-Xin Zhang, Yu-Zhuan Xu, Dong-Mei Li, Yan-Hong Luo, Qing-Bo Meng Natural polysaccharide Konjac glucomannan (KGM) is, for the first time, applied as the polymer matrix for thin film gel electrolyte in CdS/CdSe quantum dot-sensitized solar cells (QDSCs). The predominance of this thin film quasisolid state QDSCs lies in the in-situ preparation of the electrolyte and Cu2S counter electrode in one step without mold, which can significantly simplify the cell fabrication process. The cell based on this electrolyte presents an energy conversion efficiency of 4.0% under AM 1.5 illumination of 100 mW cm−2 with excellent stability compared to that of liquid-based QDSCs. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 147 PUBLICATIONS The direct dissolution of Ce2(CO3)3 and electrochemical deposition of Ce species using ionic liquid trimethyl-n-butylammonium bis(trifluoromethanesulfonyl) imide containing bis(trifluoromethanesulfonyl) imide Electrochimica Acta, 89, 1 February 2013, 144-151 David W. Hatchett, Janelle Droessler, John M. Kinyanjui, Beatriz Martinez, Kenneth R. Czerwinski Ionic liquids (ILs) are solutions comprised of cation/anion pairs that are not limited by the electrochemical side reactions common to aqueous solution. The high stability of the ionic liquid provides large potential windows that can encompass the thermodynamic potentials for the reduction of f-elements such as cerium to metal. The direct dissolution of Ce2(CO3)3·xH2O into the ionic liquid trimethyl-n-butylammonium bis(trifluoromethanesulfonyl)imide [Me3NBu][TFSI] using conjugate acid bis(trifluoromethanesulfonyl)imide [HTFSI] is demonstrated. The displacement of carbonate ligand and formation of carbonic acid facilitates the in situ dissolution. The subsequent coordination of Ce with the TFSI ion in the IL is monitored using UV/vis spectroscopy and emergent ligand to metal transitions below 300 nm. Further evidence of the coordination of Ce in the ionic liquid is based on changes in the IR spectra for absorbance bands related to the sulfonyl functional groups of the TFSI anion. The reduction/oxidation of soluble Ce in IL is examined at Au, Pt, and GC (glassy carbon) electrodes. Multi-wave voltammetry at all three electrodes is consistent with the reductive deposition of Ce species from the IL solution. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) confirm the deposition of Ce species at mica/Au electrodes. Fabrication of macroporous Pt and PtAu electrodes for electrochemical application through galvanic replacement at macroporous Cu electrode electrodeposited at polystyrene template from room temperature ionic liquid Electrochimica Acta, 89, 1 February 2013, 180-190 Shu-Jian Huang, Po-Yu Chen Macroporous Pt and PtAu electrodes (MP-Pt and MP-PtAu) were prepared through galvanic replacement at macroporous Cu electrodes, which were formed by electrodeposition of Cu at Au-coated indium tin oxide (Au/ITO) electrodes covered with ordered arrays of polystyrene (PS) nanospheres (PS/Au/ITO) in Nbutyl-N-methylpyrrolidinium dicyanamide room temperature ionic liquid (BMPDCA RTIL). After dissolving the PS templates in tetrahydrofuran (THF), macroporous Cu electrodes (MP-Cu/Au/ITO; denoted as MP-Cu hereafter) were obtained. The surface of a MP-Cu was spontaneously replaced by Pt or Pt/Au when a MP-Cu was immersed in an aqueous solution containing H2PtCl6 or H2PtCl6/HAuCl4 to form the MP-Pt (actually, MP-Pt/Cu/Au/ITO) or MP-PtAu electrodes. The atomic ratios of Au in PtAu could be adjusted by changing the ___________________________________________________________________________ page 148 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS concentration of HAuCl4 in the mixtures of H2PtCl6/HAuCl4. The electrodeposition potential, the time of replacement reaction, the concentrations of H2PtCl6 and HAuCl4, and the content of surfactant, which influence the structure of macroporous electrodes, were investigated. The surface morphologies of these macroporous electrodes were characterized with scanning electron microscope (SEM). MP-PtAu electrodes showed the better performance than the MP-Pt electrodes on the electrocatalytic oxidation of ethanol in alkaline solutions. Electrochemical performance of trimethylolpropane trimethylacrylatebased gel polymer electrolyte prepared by in situ thermal polymerization Electrochimica Acta, 89, 1 February 2013, 334-338 Dong Zhou, Li-Zhen Fan, Huanhuan Fan, Qiao Shi Cross-linked trimethylolpropane trimethylacrylate-based gel polymer electrolytes (GPE) were prepared by in situ thermal polymerization. The ionic conductivity of the GPEs are >10−3 S cm−1 at 25 °C, and continuously increased with the increase of liquid electrolyte content. The GPEs have excellent electrochemical stability up to 5.0 V versus Li/Li+. The LiCoO2|TMPTMAbased GPE|graphite cells exhibit an initial discharge capacity of 129 mAh g−1 at the 0.2C, and good cycling stability with around 83% capacity retention after 100 cycles. Both the simple fabricating process of polymer cell and outstanding electrochemical performance of such new GPE make it potentially one of the most promising electrolyte materials for next generation lithium ion batteries. Study of the formation process and the characteristics of tantalum layers electrodeposited on Nitinol plates in the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid Electrochimica Acta, 89, 1 February 2013, 346-358 A. Maho, J. Delhalle, Z. Mekhalif Thanks to excellent mechanical and biochemical properties, the nickel–titanium shape memory alloy (Nitinol) constitutes an increasingly praised platform material in dental, cardiovascular and orthopedic biomedical devices. In order to strengthen their protective abilities toward corrosion, to reinforce their biocompatibility and to confer them specific osseointegrative capacities, Nitinol plates are covered with a thin tantalum layer by electrodeposition in the 1-butyl1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid. XPS and SEM/EDX analyses highlight the chemical and morphological characteristics of the deposits: notably, these present an intrinsic dimpled nanometric structuration which is particularly remarkable considering the “soft” experimental conditions and very interesting for fundamental and applied bioactive perspectives. The present study investigates the specific and synergic effects of the Ni occurrence on the surface of the Nitinol substrates, the presence of fluorine species in the working bath, and the electrodeposition duration on the resulting formation ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 149 PUBLICATIONS process, morphology and chemical composition of the tantalum coating. Finally, samples are submitted to electrochemical characterizations and in vitro hydroxyapatite growth tests for a primary assessment of their corrosion resistance and osseoinductive features. Lithium polymer cell assembled by in situ chemical cross-linking of ionic liquid electrolyte with phosphazene-based cross-linking agent Electrochimica Acta, 89, 1 February 2013, 359-364 Ji-Ae Choi, Yongku Kang, Dong-Won Kim Ionic liquid-based cross-linked gel polymer electrolytes were prepared with a phosphazene-based cross-linking agent, and their electrochemical properties were investigated. Lithium polymer cells composed of lithium anode and LiCoO2 cathode were assembled with ionic liquid-based cross-linked gel polymer electrolyte and their cycling performance was evaluated. The interfacial adhesion between the electrodes and the electrolyte by in situ chemical crosslinking resulted in stable capacity retention of the cell. A reduction in the ionic mobility in both the electrolyte and the electrode adversely affected discharge capacity and high rate performance of the cell. DSC studies demonstrated that the use of ionic liquid-based cross-linked gel polymer electrolytes provided a significant improvement in the thermal stability of the cell. Anti-thermal shrinkage nanoparticles/polymer and ionic liquid based gel polymer electrolyte for lithium ion battery Electrochimica Acta, 89, 1 February 2013, 461-468 Youhao Liao, Changjuan Sun, Shejun Hu, Weishan Li A new gel polymer electrolyte (GPE) system for lithium ion battery was developed by using anti-thermal shrinkagable nanoparticles/polymer incorporating with ionic liquid. Polyethylene-supported SiO2/poly(methyl methacrylate–acrylonitrile–vinyl acetate) (P(MMA–AN–VAc)) and Al2O3/P(MMA–AN–VAc) separators were prepared and the corresponding GPEs, SiO2/P(MMA–AN–VAc) + LiTFSI + PYR14TFSI/VC and Al2O3/P(MMA–AN–VAc) + LiTFSI + PYR14TFSI/VC, were obtained by immersing the separators in an ionic liquid electrolyte of 0.5 mol kg−1 LiTFSI in PYR14TFSI/VC. The structure and performance of the separators and corresponding GPEs were characterized by thermogravimetric analysis (TGA), air permeability, scanning electron spectroscopy (SEM), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), cyclic voltammetry (CV) and charge–discharge test. It is found that the nanoparticles/polymer separators have good dimensional stability and the corresponding GPEs have good ionic conductivity and excellent compatibility with the electrodes of lithium ion battery. SiO2/P(MMA–AN–VAc) and Al2O3/P(MMA–AN–VAc) separators are stable up to 310 °C and have a Gurley value of 8 s. SiO2/P(MMA–AN–VAc) based GPE has an ionic conductivity of ___________________________________________________________________________ page 150 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS 1.2 × 10−3 S cm−1 at room temperature and an oxidative decomposition potential of 5.3 V (vs. Li/Li+). The interfacial resistance between anode lithium and GPE is changed from 47 Ω cm2 on the first day to 118 Ω cm2 after the 25 days. The battery Li/GPE/LiFePO4 shows good rate and cyclic performance. Electrodeposition of zinc films from ionic liquids and ionic liquid/water mixtures Electrochimica Acta, 89, 1 February 2013, 635-643 Z. Liu, S. Zein El Abedin, F. Endres The electrodeposition of zinc films from zinc triflate (Zn(TfO)2) in two air and water stable ionic liquids namely, 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate, [Py1,4]TfO, and 1-ethyl-3-methylimidazolium trifluoromethylsulfonate, [EMIm]TfO, was studied. The influence of water on the deposition process was also investigated. The morphology of the obtained deposit is different in the two liquids. Dense and uniform silvery zinc deposits with good adherence were obtained from [EMIm]TfO while less adhering and dark gray zinc deposits were obtained from [Py1,4]TfO. The SEM results of the deposit obtained from [EMIm]TfO revealed a hexagonal zinc structure while a flower-like structure was observed for the deposits obtained from [Py1,4]TfO under the same conditions. Water added to the electrolyte has a distinct effect on the deposits obtained in [EMIm]TfO and [Py1,4]TfO, respectively. The difference in the structure might be attributed to the different interaction of the ions with the substrate. Furthermore, the addition of water to the solution decreases the electrochemical window of both ionic liquids and shifts the reduction of zinc(II) to less negative values. The XRD phase analysis showed that not only Zn was deposited in the dried ionic liquids also Zn-Au alloys were obtained. However, in ionic liquid/water mixtures only Zn was obtained, surprisingly. Furthermore, Zn deposits obtained at 50 °C showed a preferential orientation compared with those ones obtained at room temperature. Both the water concentration and the temperature affect the deposition process. Internal redox amidation of α,β-unsaturated aldehydes in ionic liquids. The electrochemical route Electrochimica Acta, 89, 1 February 2013, 692-699 Marta Feroci, Isabella Chiarotto, Achille Inesi A simple, N-heterocyclic carbene (NHC) activated synthesis of amides has been performed via electrolysis, carried out under galvanostatic control, of an ionic liquid (Bmim-BF4) followed by addition to the catholyte of an α,β-unsaturated aldehyde and amine. Amides have been isolated, in good to elevated yields, in the absence of any base, co-catalyst and organic solvent. The selectivity of amidation, versus the formation of imine as by-product, has been related to the molar ratio electrogenerated NHC/aldehyde. The results, obtained using ionic ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 151 PUBLICATIONS liquids and electrochemical procedures, have been compared with those obtained using organic solvents and classical procedures. Electrochemical behavior of Zn/Zn(II) couples in aprotic ionic liquids based on pyrrolidinium and imidazolium cations and bis(trifluoromethanesulfonyl)imide and dicyanamide anions Electrochimica Acta, 89, 1 February 2013, 756-762 M. Xu, D.G. Ivey, Z. Xie, W. Qu Motivated by the potential of using room temperature ionic liquids (RTILs) as electrolytes to replace traditional aqueous electrolytes for Zn-anode secondary batteries, Zn/Zn(II) redox reactions have been studied in four aprotic RTILs based on pyrrolidinium ([Pyrr]+) and imidazolium ([Im]+) cations, and bis(trifluoromethanesulfonyl)imide ([TFSI]−) and dicyanamide ([DCA]−) anions. Cyclic voltammetry results suggest a smaller overpotential for Zn redox in [Im]+ cation based and [DCA]− anion based RTILs than in [Pyrr]+ and [TFSI]− based RTILs. Potentiodynamic polarization experiments indicate a strong dependence of the electrode reaction mechanism for the Zn species on the RTIL anions. In [TFSI]− based RTILs, Zn2+ ions are the electroactive species, with the electrode reaction being a single-step, two-electron transfer process. In [DCA]− based RTILs, two-step, single-electron reactions account for the electrode mechanism. The exchange current densities derived from Tafel analysis for the Zn species in the four RTILs are greater than 10−3 mA/cm2, with the [Im]+ cation based RTIL possessing the highest value of 9.9 × 10−3 mA/cm2. The results obtained will assist in obtaining a better understanding of the electrochemical behavior of Zn in RTILs, shedding light on the development of RTILs for Zn-anode secondary batteries. Supercapacitive properties of activated carbon electrode in organic electrolytes containing single- and double-cationic liquid salts Electrochimica Acta, 89, 1 February 2013, 807-813 Won-Je Cho, Chul Gi Yeom, Byung Chul Kim, Kwang Man Kim, Jang Myoun Ko, Kook-Hyun Yu A series of novel room-temperature ionic liquid (RTIL) salts based on Cn(MIm)iA and Cn(TMA)iA (i = 1, 2 as single- and double-cation form, respectively; n = 4, 5, 6; A = BF4−, TFSI−), where MIm, TMA, and TFSI indicate 3-methylimidazolium, trimethylammonium, and bis(trifluoromethanesulfonyl)imide, respectively, are synthesized varying the number of alkyl chains, e.g., butane (n = 4), pentane (n = 5), and hexane (n = 6) in the main backbone. Ionic conductivities of each RTIL salt are measured after dissolving with propylene carbonate (PC) or acetonitrile (ACN) at the salt concentration of 0.5 M. A supercapacitor containing activated carbon as an active material in the organic electrolyte containing ionic liquid salts is ___________________________________________________________________________ page 152 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS fabricated to evaluate the supercapacitive properties using cyclic voltammetry. It is found that the effects of counter-anions (BF4− and TFSI−) and the number of cations (single- and double-cation) in RTIL salts on the supercapacitive property are of importance in determining their potential applications for energy storage devices. Gel electrolytes based on ionic liquids for advanced lithium polymer batteries Electrochimica Acta, 89, 1 February 2013, 823-831 Andreas Hofmann, Michael Schulz, Thomas Hanemann A new ionic liquid-based polymer gel electrolyte for lithium ion batteries is prepared by combining N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)azanide, organic carbonates, lithium bis(trifluoromethylsulfonyl)azanide, and poly(vinylidene fluoride-cohexafluoropropylene). The conductivities of the gel electrolytes at room temperature are about 1–2 mS/cm. It is shown that the polymer gel electrolytes work effectively with a graphite anode and a LiCo1/3Mn1/3Ni1/3O2 cathode. Further it is proven that the addition of vinylene carbonate and 4-vinylpyridine considerably improves the cell performance. Effects of water and ethanol on the electrical conductivity of caprolactam tetrabutyl ammonium halide ionic liquids Journal of Molecular Liquids, 178, February 2013, 1-4 ErHong Duan, YaNan Guan, Bin Guo, MiaoMiao Zhang, Di Yang, Kun Yang To determine the structure of caprolactam tetrabutyl ammonium halide (F, Cl and Br) ionic liquids and the interaction of ionic liquids and solvents (water and ethanol), the effects of solvents on the electrical conductivity of ionic liquids were investigated at atmospheric pressure and temperatures from 293.15 to 333.15 K. The electrical conductivity of ionic liquids increases with an increase in temperature, and the anion electronegativity decreases in the following order: F > Cl > Br. The electrical conductivity of the binary system of ionic liquid and solvents (water and ethanol) appears to decrease slightly with an increase in temperature. The electrical conductivity of the caprolactam tetrabutyl ammonium halide ionic liquid solutions is much larger than the electrical conductivity of the pure ionic liquids under the same conditions. The electrical conductivity of aqueous solutions of ionic liquids is very different from the electrical conductivity of ethanol solutions. Separation/preconcentration of trace copper by extraction into [C4mim] [PF6] RITL containing p-tert-butyl-calix[4]arene functionalized with ophenanthroline prior to flame absorption atomic spectrometry Journal of Molecular Liquids, 178, February 2013, 20-24 Lina Ma, Xiashi Zhu, Wenjun Wang ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 153 PUBLICATIONS A liquid–liquid extraction (LLE)-flame atomic absorption spectrometry (FAAS) for the separation/analysis of copper has been developed. The method was based on the fact that the inclusion complex of copper(II) with 25, 27-di (5phenanthrolinylaminocarbonylmethoxy)-26,28-dihydroxy-p-tertbutylcalix[4]arene (TBCP) could be extracted into room temperature ionic liquids (RTILs, 1-butyl-3-methylimidazolium hexafluoro-phosphate [C4mim] [PF6] as the green extractant, TBCP as the complexlant), and the copper(II) was subsequently determined by FAAS. The LLE was optimized in detail. The selectivity and mechanism of LLE were approached. Under optimized experimental conditions, the linear range of calibration curve for the determination of copper(II) was 0.020–10.0 µg/mL. The detection limit estimated (S/N = 3) was 3.59 ng/mL with 3.0% RSD. It has been applied for the determination of copper(II) in water samples with satisfactory results. Conductivity and viscosity properties of associated ionic liquids phosphonium orthoborates Journal of Molecular Liquids, 178, February 2013, 57-62 Alejandro García, Luis C. Torres-González, Karinjilottu P. Padmasree, Maria G. Benavides-Garcia, Eduardo M. Sánchez A new group of room temperature molten salts based on asymmetric isobutyl(trihexyl)phosphonium cation with different chelated orthoborate anions are presented in this report. The physicochemical properties of these compounds as glass transition temperature, thermal stability, viscosity and conductivity are determined and discussed on structural basis. The highest room temperature conductivity observed was for the isobutyl(trihexyl)phosphonium bis(malonate)borate. The results indicate that the prepared orthoborates have lower viscosities, better conductivities when compared to their precursor, isobutyl(trihexyl)phosphonium bromide. Our investigation has found that those new compounds have an intermediate-to-fragile behavior. We plotted the conductivity and viscosity data according to Walden's rule and found that they can be classified as an associated ionic liquid (AIL) an intermediate between a true ionic liquid and a molecular species. Synthesis, characterization and application of ionic liquid 1,3-disulfonic acid imidazolium hydrogen sulfate as an efficient catalyst for the preparation of hexahydroquinolines Journal of Molecular Liquids, 178, February 2013, 113-121 Abdolkarim Zare, Fereshteh Abi, Ahmad Reza Moosavi-Zare, Mohammad Hassan Beyzavi, Mohammad Ali Zolfigol In this work, novel Brønsted acidic ionic liquid 1,3-disulfonic acid imidazolium hydrogen sulfate {[Dsim]HSO4} is synthesized, and characterized by studying its FT-IR, 1H NMR, 13C NMR, mass, TG, DTG and XRD spectra. This ionic ___________________________________________________________________________ page 154 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS liquid, with three acidic functional groups, is utilized as a highly efficient, homogeneous and reusable catalyst for the preparation of hexahydroquinolines via one-pot multi-component condensation of arylaldehydes, dimedone (5,5dimethylcyclohexane-1,3-dione), β-ketoesters and ammonium acetate under solvent-free conditions. The catalyst can form dual hydrogen-bond using its SO3H groups which this subject can direct to its assembly and efficiency. Glucose-based deep eutectic solvents: Physical properties Journal ofMolecular Liquids, 178, February 2013, 137-141 Adeeb Hayyan, Farouq S. Mjalli, Inas M. AlNashef, Yahya M. Al-Wahaibi, Talal Al-Wahaibi, Mohd Ali Hashim Deep eutectic solvents (DESs) are considered nowadays as green ionic liquid (IL) analogues. Despite their relatively short period of introduction as a special class of ILs, they have been under an increasing emphasis by the scientific community due to their favorable properties. In the present study, a glucose based DES of choline chloride (2-hydroxyethyl-trimethylammonium chloride) with the monosaccharide sugar d-glucose anhydrous was synthesized at different molar ratios. The physical properties of density, viscosity, surface tension, refractive index, and pH were measured and analyzed as function of temperature in the practical temperature range of 298.15–358.15 K. The analysis of these physical properties revealed that these novel DESs have the potential to be utilized for several possible industrial applications involving processing and separation of food constituents, pharmaceutical applications, as well as mediums for chemical reactions. Slow molecular mobility in the amorphous solid and the metastable liquid states of three 1-alkyl-3-methylimidazolium chlorides Journal of Molecular Liquids, 178, February 2013, 142-148 Hermínio P. Diogo, Susana S. Pinto, Joaquim J. Moura Ramos The slow molecular mobility in three ionic liquids, 1-alkyl-3-methylimidazolium chlorides with alkyl tails C4, C6 and C8, has been investigated by thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC), in a temperature interval including the amorphous solid and the supercooled liquid state. A specific feature of these ionic liquids, compared with typical molecular liquids, is the existence of a slow relaxation close to the main relaxation but above Tg, which is cooperative and shows a high dielectric strength. Thermodynamic properties of aqueous solutions of two ammonium-based protic ionic liquids at 298.15 K Journal of Molecular Liquids, 178, February 2013, 149-155 Mengyin Hou, Yingjie Xu, Yajuan Han, Bin Chen, Wenxia Zhang, Qinghua Ye, Jinzhi Sun ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 155 PUBLICATIONS Densities (ρ), refractive indices (nD) and electrical conductivities (κ) of ethylammonium acetate (N2Ac) protic ionic liquid + water and propylammonium acetate (N3Ac) protic ionic liquid + water binary mixtures over the entire composition range were measured at 298.15 K under atmospheric pressure. The excess molar volumes (VE), apparent molar volumes (Vϕi), partial molar volumes () and excess partial molar volumes () of the binary mixtures were calculated from the density data. The refractive index deviations (ΔnD) of the binary mixtures were determined using the refractive index data. The excess molar volumes and refractive index deviations were correlated with the Redlich– Kister equation. The excess molar volumes of the above-mentioned systems are negative over the whole composition range, while the refractive index deviations are positive. The concentration dependence of electrical conductivity was fitted according to the empirical Casteel–Amis equation. The intermolecular interactions and structural effects were analyzed on the basis of the measured and the derived properties. Electrospun poly(vinylidene fluoride)/poly(methyl methacrylate) grafted TiO2 composite nanofibrous membrane as polymer electrolyte for lithiumion batteries Journal of Power Sources, 223, 1 February 2013, 206-213 Wei-Wei Cui, Dong-Yan Tang, Zai-Lin Gong An organic/inorganic hybrid nanocomposite, poly(methyl methacrylate) grafted titanium dioxide (PMMA-g-TiO2), is synthesized by atom transfer radical polymerization (ATRP). The hybrid nanocomposites are incorporated into poly(vinylidene fluoride) (PVdF) membranes during the electrospinning process to fabricate a composite nanofibrous membrane. Then the resultant fibrous polymer electrolyte is obtained by immersing the composite membrane into liquid electrolyte. FTIR, TEM, TGA, GPC, SEM, XRD, and DSC are used to characterize the structure, morphology and thermal properties of PMMA-g-TiO2 hybrid nanocomposite and the composite nanofibrous membrane. The composite nanofibrous membrane is proven to be a good absorbent for the liquid electrolyte, and it exhibits a high electrolyte uptake and a high electrolyte retention ratio. The incorporation of PMMA-g-TiO2 into the nanofibrous membrane inhibits the crystallization of PVdF during the solidification process and improves the ionic conductivity of the fibrous polymer electrolyte from 2.51 × 10−3 to 2.95 × 10−3 S cm−1 at 20 °C. The electrochemical stability window of the polymer electrolyte is also enhanced due to the presence of PMMA-gTiO2. Nucleic acid bases in 1-alkyl-3-methylimidazolium acetate ionic liquids: A thermophysical and ionic conductivity analysis The Journal of Chemical Thermodynamics, 57, February 2013, 1-8 ___________________________________________________________________________ page 156 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS J.M.M. Araújo, A.B. Pereiro, F. Alves, I.M. Marrucho, L.P.N. Rebelo The use of ionic liquids as a media for dissolving DNA holds great promise for the development of new base materials in electrochemistry. This paper reports the systematic study of the effect of two nucleic acid bases, uracil and adenine, on the ionicity of 1-alkyl-3-methylimidazolium acetates achieved by monitoring several thermodynamic and transport properties. Density, dynamic viscosity, speed of sound, refractive index and ionic conductivity of 1-ethyl-3methylimidazolium acetate and 1-butyl-3-methylimidazolium acetate were studied as a function of temperature at atmospheric pressure. The thermal expansion coefficients and molar volumes of these ionic liquids were calculated from the experimental density values. The various properties of the binary mixtures 1-ethyl-3-methylimidazolium acetate with uracil or adenine, namely, their ionic conductivity, density and viscosity in the temperature range 298 K– 343 K were determined as a function of the nucleobase content. Walden plots were determined and used to clarify the role of the nucleobases in the ionic liquids ionicity. Henry’s constants and activity coefficients of some organic solutes in 1butyl,3-methylimidazolium hydrogen sulfate and in 1-methyl,3trimethylsilylmethylimidazolium chloride The Journal of Chemical Thermodynamics, 57, February 2013, 178-181 Brian Yoo, Waheed Afzal, John M. Prausnitz Using a customized capillary gas–liquid chromatography column, Henry’s constants and activity coefficients at infinite dilution are reported for benzene, toluene, ethyl acetate, 1,4-dioxane, 1,2-dimethoxyethane, acetonitrile, nitromethane, tetrahydrofuran, chloroform, methanol, ethanol, and 1-propanol in ionic liquids 1-butyl,3-methylimidazolium hydrogen sulfate [BMIM][HSO4] and 1-methyl,3-trimethylsilylmethylimidazolium [SiMIM][Cl] chloride from 313 to 413 K. These acidic ionic liquids may provide suitable media for acid-catalyzed chemical reactions. Thermophysical properties of ionic liquid {1-butyl-3-methylimidazolium bromide [bmim][Br] in alkoxyalkanols + water} mixtures at different temperatures The Journal of Chemical Thermodynamics, 57, February 2013, 182-188 Amalendu Pal, Harsh Kumar, Bhupinder Kumar, Pooja Sharma, Kirtanjot Kaur The interactions of alkoxyalkanols with the ionic liquid 1-butyl-3methylimidazolium bromide [bmim][Br] as a function of temperature were investigated by combination of volumetric and acoustic methods. The density, ρ, and speed of sound, u, of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether (0.00– 1.01 mol·kg−1) in aqueous 1-butyl-3-methylimidazolium bromide solutions ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 157 PUBLICATIONS ranging from pure water to 0.29 mass% of ionic liquid have been measured at T = (288.15, 298.15 and 308.15) K and atmospheric pressure. The apparent molar (Vϕ) and adiabatic compressibility (Kϕ,S) of alkoxyalkanols in aqueous ionic liquid solution were determined at the measured temperatures. The partial molar and partial molar adiabatic compressibility of alkoxyalkanols at infinite dilution were evaluated. Transfer volumes and transfer adiabatic compressibility () at infinite dilution from water to aqueous ionic liquid solution were also calculated. The temperature dependence of the apparent molar was used to calculate apparent molar expansivity () and the Hepler’s constant values, . The results were explained on the basis of competing patterns of interactions of cosolvent and the solute. Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(2-methoxyethyl)-1methylpiperidinium trifluorotris(perfluoroethyl)phosphate The Journal of Chemical Thermodynamics, 57, February 2013, 197-202 Andrzej Marciniak, Michał Wlazło This work is continuation of our systematic study of activity coefficients at infinite dilution, γ∞ of different organic solutes and water in the ionic liquids. New data of γ∞ were determined for 62 solutes, including alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, 1-nitropropane, butanal, acetonitrile, and water in the ionic liquid 1-(2-methoxyethyl)-1-methylpiperidinium trifluorotris(perfluoroethyl)phosphate by inverse gas chromatography at the temperature range from (318.15 to 368.15) K. The basic thermodynamic functions, namely partial molar excess Gibbs free energies, , enthalpies, and entropies, at infinite dilution were calculated from the experimental γ∞ values obtained over the temperature range. Additionally the gas–liquid partition coefficients, KL were determined. Results are compared to previously investigated ionic liquids with the same cations or anions. Values of the selectivity and capacity at infinite dilution for heptane/benzene, heptane/thiophene, and heptane/methanol extraction problems were calculated from experimental γ∞ values to verify the possibility of investigated ionic liquid as an entrainer in liquid–liquid extraction. Effect of the ethoxy groups distribution on the phase behaviour of the binary systems carbon dioxide CO2 with industrial non-ionic surfactants (CiEOj) The Journal of Chemical Thermodynamics, 57, February 2013, 224-229 Tania E. Sandoval, M. Pilar Gárate, J. Scavia, Louw J. Florusse, Cor J. Peters Solubility experiments of industrial ethoxylated surfactants denoted as CiEOj (where Ci = hydrocarbon tail, EOj = oxyethylene groups, i = 6–8 and j = 3–5) in ___________________________________________________________________________ page 158 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS sub-and supercritical carbon dioxide were carried out at different temperatures, pressures and concentrations in a Cailletet apparatus as a representative model for dry cleaning system. For the study, industrial surfactants with an ethoxy group distribution were used to replicate the actual dry-cleaning process. For a variety of compositions, results are reported for binary systems within temperature and pressure ranges of 260–310 K and 2.0–10 MPa respectively. In each experiment the surfactants reach equilibrium with carbon dioxide at different concentrations. The data show that with all the surfactants upon increasing concentration, the liquid–liquid curve shifts to lower temperatures. Therefore, the one-phase solution gap is reduced in pressure and temperature at higher concentrations. When the length of the hydrocarbon tail remains constant and the ethoxylated chain is increased from three to five groups, the LL curve once again shifts to lower temperatures and the two phases start earlier. This effect can be attributed to the higher surfactant’s polarity due to the increase in j. On the other hand, when the number of ethoxylated group’s j remains constant and the length of the hydrocarbon tail is increased from six to eight carbon atoms, there is also a significant shift in the LL curve. That signals the fact that the appearance of two phases is also related with the length of the hydrocarbon chain and therefore the surfactant structure itself. These results differ from the trend presented for the pure surfactants in CO2 and can be attributed to the ethoxy group distribution of the industrial type surfactants. Physics and chemistry of an ionic liquid in some industrially important solvent media probed by physicochemical techniques The Journal of Chemical Thermodynamics, 57, February 2013, 230-237 Mahendra Nath Roy, Ishani Banik, Deepak Ekka Electrolytic conductivities (Λ), densities (ρ), viscosities (η), and ultrasonic speed (u) of an ionic liquid (IL) tetrabutylphosphonium tetrafluoroborate [Bu4PBF4] have been studied in dimethylsulfoxide (DMSO), dimethylacetamide (DMA), and dimethylformamide (DMF) at T = 298.15 K. The limiting molar conductivity (), the association constant (KA), and the distance of closest approach of ions (R) have been evaluated using the Fuoss conductance equation (1978). The molar conductivities Electrolytic conductivities (Λ), densities (ρ), viscosities (η), and ultrasonic speed (u) of an ionic liquid (IL) tetrabutylphosphonium tetrafluoroborate [Bu4PBF4] have been studied in dimethylsulfoxide (DMSO), dimethylacetamide (DMA), and dimethylformamide (DMF) at T = 298.15 K. The limiting molar conductivity (Λ0), the association constant (KA), and the distance of closest approach of ions (R) have been evaluated using the Fuoss conductance equation (1978). The molar conductivities observed were explained by the formation of ion-pairs (M+ + X− ↔ MX). The Walden product is obtained and discussed. Ion–solvent interactions have been interpreted in terms of apparent molar volumes ( V) and viscosity B-coefficients which are obtained from the results supplemented with densities and viscosities, respectively. The limiting apparent molar volumes ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 159 PUBLICATIONS ( V0), experimental slopes (SV∗) derived from the Masson equation and viscosity A and B coefficients using the Jones–Dole equation have been interpreted in terms of ion–ion and ion–solvent interactions respectively. The adiabatic compressibility (β) has been evaluated using the ultrasonic speed (u) values. Finally values of the limiting partial molar adiabatic compressibility ( K0 ) are calculated and discussed. Desulfurization of fuel-oils with [C2mim][NTf2]: A comparative study The Journal of Chemical Thermodynamics, 57, February 2013, 248-255 B. Rodríguez-Cabo, A. Soto, A. Arce A tendency to use polysubstituted pyridinium-based ionic liquids for desulfurization of fuel-oils is being very remarkable during last years. Are these ones the most suitable ionic liquids for this purpose? The possibility of using a much cheaper ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, has been studied in this work. With this aim, LLE data of the {[C2mim][NTf2] + thiophene + toluene}, {[C2mim][NTf2] + thiophene + n-hexane} and {[C2mim][NTf2] + pyridine + nhexane} ternary systems have been obtained at T = 298.15 K and atmospheric pressure. The NRTL and UNIQUAC models have been used to correlate the obtained data. Solute distribution ratios and selectivities have been calculated and a comparison with data obtained previously for other ionic liquids has been established. It was found that both cation and anion clearly affect to these thermodynamic parameters. According not just to solubility, but also in terms of selectivity and cost, [C2mim][NTf2] can be a competitive desulfurization solvent. Thermodynamic modeling of the (Al2O3 + Na2O), (Al2O3 + Na2O + SiO2), and (Al2O3 + Na2O + AlF3 + NaF) systems The Journal of Chemical Thermodynamics, 57, February 2013, 306-334 Guillaume Lambotte, Patrice Chartrand All available thermodynamic and phase diagram data for the condensed phases of the (Al2O3 + Na2O), (Al2O3 + Na2O + SiO2), and (Al2O3 + Na2O + AlF3 + NaF) systems have been critically assessed. Model parameters for solid solutions and a single set of parameters for the liquid solution in the binary, ternary, and ternary reciprocal systems have been optimized and permit to reproduce most of the critically reviewed experimental data. The Modified Quasichemical Model in the Quadruplet Approximation was used for the oxyfluoride (mixture of molten oxides and salts) liquid solution, which exhibits strong first-nearest-neighbor and second-nearest-neighbor shortrange order. This thermodynamic model takes into account both types of shortrange order as well as the coupling between them. The charge compensation ___________________________________________________________________________ page 160 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS effect present in the (Al2O3 + Na2O + SiO2) system was taken into account by adding a (NaAl)4+ species in the liquid solution. Interactions of volatile organic compounds with the ionic liquids 1-butyl-1methylpyrrolidinium tetracyanoborate and 1-butyl-1-methylpyrrolidinium bis(oxalato)borate The Journal of Chemical Thermodynamics, 57, February 2013, 344-354 Aleš Blahut, Vladimír Dohnal Interactions of volatile organic compounds with two ionic liquids (ILs) 1-butyl1-methylpyrrolidinium tetracyanoborate [BMPYR][B(CN)4] and 1-butyl-1methylpyrrolidinium bis(oxalato)borate [BMPYR][BOB] were explored through systematic GLC retention measurements. Infinite dilution activity coefficients and gas–liquid partition coefficients of 30 selected solutes in [BMPYR][B(CN)4] and [BMPYR][BOB] were determined at five temperatures in the range from (318.15 to 353.15) K and from (333.15 to 373.15) K, respectively. Partial molar excess enthalpies and entropies at infinite dilution were derived from the temperature dependence of the values. The Linear Free Energy Relationship (LFER) solvation model was used to correlate successfully the values. The LFER correlation parameters and excess thermodynamic functions were analyzed to disclose molecular interactions operating between the ILs and the individual solutes. Among other ILs, [BMPYR][B(CN)4] was identified as a very weakly cohesive solvent medium, in contrast to [BMPYR][BOB] which appears to be fairly cohesive IL close in this respect to [BMPYR][DCA] examined recently. Both [BMPYR][B(CN)4] and [BMPYR][BOB] are capable of interacting specifically through all modes (lone electron pairs, dipolarity/polarizibility, and hydrogen bonding) with solutes of complementary capabilities. Their hydrogen bond basicity and ability to interact with lone electron pairs are appreciable but distinctly lower than those of [BMPYR][DCA]. The proton donating capability of these ILs is weak, but still traceable, and stems undoubtedly from unsubstituted hydrogen atoms on the pyrrolidinium ring of their cation. The selectivities of [BMPYR][B(CN)4] and [BMPYR][BOB] for separation of aromatic hydrocarbons and thiophene from saturated hydrocarbons rank among [BMPYR] ILs the lowest and medium, respectively. The selectivity of [BMPYR][B(CN)4] is comparable to that of sulfolane, but this IL surpasses it roughly three times in the capacity. [BMPYR][B(CN)4] and [BMPYR][BOB] could also serve as efficient entrainers in separations of other non-petrochemical azeotropic systems of industrial importance by extractive distillation. In particular, we have identified [BMPYR][B(CN)4] as a very convenient separation agent for (methanol + dimethyl carbonate) mixture. Solubility of CO2 in amide-based Brønsted acidic ionic liquids The Journal of Chemical Thermodynamics, 57, February 2013, 355-359 Dongshun Deng, Yanhong Cui, Dong Chen, Ning Ai ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 161 PUBLICATIONS Several hydrophilic amide-based Brønsted acidic ionic liquids (BAILs) were prepared by simple acid-base neutralization reaction of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP) with trifluoroacetic acid (TFA) or tetrafluoroboric acid (FBA). The solubility data of CO2 in these BAILs were determined at T = (303.15, 313.15, and 323.15) K and subatmospheric pressure using isochoric saturation method. With the same cation, CO2 solubility in TFA-based BAILs was higher than that in FBA-based ones. From the variation of solubility, expressed as Henry’s law constants, with temperature, the standard Gibbs free energy, enthalpy, and entropy changes of CO2 solvation were calculated. The solubilities of CO2 in these BAILs were apparently increased with increasing the molar of BAIL except for [DMFH][TFA]. Surface tension and refractive index of pure and water-saturated tetradecyltrihexylphosphonium-based ionic liquids The Journal of Chemical Thermodynamics, 57, February 2013, 372-379 Hugo F.D. Almeida, José A. Lopes-da-Silva, Mara G. Freire, João A.P. Coutinho Experimental data on the surface tension and refractive index of tetradecyltrihexylphosphonium-based ionic liquids with bromide, chloride, decanoate, methanesulfonate, dicyanimide, bis(2,4,4trimethylpentyl)phosphinate and bis(trifluoromethylsulfonyl)imide anions are reported. The data were obtained for pure and water saturated samples at temperatures from 283 K to 353 K and at atmospheric pressure. The refractive index of the investigated ionic liquids decreases with increasing the water content in the sample. On the other hand, no clearly dependence of the surface tension with the water content up to a weight fraction of 16% was found. The prediction of the refractive index for the studied ionic liquids was also accomplished by a group contribution method and new values for the cation and diverse anions were estimated and proposed. The studied ionic liquids show lower surface tension in comparison with imidazolium-, pyridinium- or pyrrolidinium-based ionic liquids with a similar anion; also they show higher surface entropy than cyclic nitrogen-based fluids which indicates a lower surface organization. The anion dependence of the surface tension and surface entropy for the investigated ionic liquids is weaker than that for short-chain imidazolium-based ionic liquids. Their critical temperatures evaluated from Eötvos and Guggenheim equations are also lower than those of N-heterocyclic ionic fluids. Thermodynamic evaluation and optimization of (NaF + AlF3 + CaF2 + BeF2 + Al2O3 + BeO) system The Journal of Chemical Thermodynamics, 57, February 2013, 387-403 Christian Robelin, Patrice Chartrand the ___________________________________________________________________________ page 162 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases and relevant gaseous species of the (NaF + AlF3 + CaF2 + BeF2 + Al2O3 + BeO) system, and optimized model parameters have been found. The (NaF + AlF3 + CaF2 + Al2O3) subsystem, which is the base electrolyte used for the electro-reduction of alumina in Hall–Héroult cells, has been critically evaluated in a previous article. The Modified Quasichemical Model in the Quadruplet Approximation for shortrange ordering was used for the molten salt phase. The thermodynamic database developed is a first step towards a quantitative study of the beryllium mass balance in an electrolysis cell. In particular, the predominant Be-containing species in the gas phase evolved at the anode were identified; and, for a given beryllium content of the alumina, the beryllium content of the electrolytic bath at steady state was assessed under several approximations. The preparation of carbon dots/ionic liquids-based electrolytes and their applications in quasi-solid-state dye-sensitized solar cells Electrochimica Acta, 88, 15 January 2013, 100-106 Huayu Xiong, Xiuhua Zhang, Binghai Dong, Hongbing Lu, Li Zhao, Li Wan, Guotian Dai, Shimin Wang A facile means to generate carbon dots/ionic liquids (ILs) blend using ionic liquid-assisted electrochemical exfoliation was demonstrated. Two kinds of ILs, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) and 1-butyl-3methylimidazolium hexafluorophosphate ([bmim][PF6]), were used in this work. Transmission electron microscopy and UV–vis spectrum were employed to characterize the formed carbon dots/ILs. The carbon dots/ILs were used for fabricating quasi-solid-state dye-sensitized solar cells (DSSCs), where 1-butyl3-methylimidazolium iodide and LiI/I2 were added to enhance the performance of DSSCs. Effects of the varied contents of components in the complex on the performance of DCCSs have been studied in detail at ambient temperature. The electrochemical impedance spectroscopy showed that the introduction of carbon dots into ionic liquids can enhance the electrical properties by facilitating charge transfer processes of the electrolytes. The overall energy-conversion efficiency (η) was 2.71% and 2.41% for carbon dots/[bmim][PF6] and carbon dots/[bmim][BF4] based blend electrolytes, respectively. A 82% enhancement in η was obtained by introduction of carbon dots into [bmim][PF6] comparing with pure [bmim][PF6] (η = 1.49%). In addition, the cells exhibited good stability under continuous illumination in room temperature without any further sealing. Preparation and characterization of gel polymer electrolytes containing Nbutyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide ionic liquid for lithium ion batteries Electrochimica Acta, 88, 15 January 2013, 147-156 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 163 PUBLICATIONS Libo Li, Jiajia Wang, Peixia Yang, Shaowen Guo, Heng Wang, Xiuchun Yang, Xuwei Ma, Shuo Yang, Baohua Wu Gel polymer electrolytes containing N-butyl-N-methylpyrrolidinum bis(trifluoromethanesulfonyl) imide (PYR14TFSI) ionic liquid are prepared by the solution casting method. Thermal and electrochemical properties have been determined for these gel polymer electrolytes. The electrical properties are investigated in detail by the linear sweep voltammetry, cyclic voltammetry and impedance spectroscopy with the aid of the equivalent circuit fitting of the impedance spectra. The results show that the studied electrolytes have good selfstanding characteristics, and also a sufficient level of thermal stability and a good electrochemical window. The conductivity increases with increasing amount of mixture, and for the studied system, the highest value of the conductivity measured at room temperature is 4.0 × 10−4 S cm−1. The lithium ions transference number reaches the maximum value when the gel electrolyte contains 33.3 wt% PYR14TFSI ionic liquid. Based on the experiments, measurements and fitting, the models describing the lithium ion transmission and the properties of electrolyte/electrode interface are developed. Electrodeposition of Cu–Li alloy from room temperature ionic liquid 1butyl-3-methylimidazolium tetrafluoroborate Electrochimica Acta, 88, 15 January 2013, 203-207 Peixia Yang, Yanbiao Zhao, Caina Su, Kaijian Yang, Bo Yan, Maozhong An Electrodeposition of Cu–Li alloy from 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) ionic liquid was investigated. The cyclic voltammetry behaviors of [BMIm][BF4] containing Cu(II), Li(I), and mixtures of Cu(II) and Li(I) were studied at a copper working electrode, separately. The Cu–Li alloy produced by direct current electrodeposition was characterized by inductively coupled plasma atomic emission spectrometry (ICP), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM). The function of 2-butyne-1,4-diol was studied by linear sweep voltammetry. The result shows that the 2-butyne-1,4-diol could improve Li content in deposit, and make the Cu–Li alloy deposits denser and finer. Chemical mixing in molten-salt for preparation of high-performance spinel lithium manganese oxides: Duplication of morphology from nanostructured MnO2 precursors to targeting materials Electrochimica Acta, 88, 15 January 2013, 756-765 Wei Xiao, Wenting Liu, Xuhui Mao, Hua Zhu, Dihua Wang The chemical mixing strategy involving molten-salt lithiation at 450 °C and post-annealing at 800 °C on formation of morphological replica of spinel lithium manganese oxides from nanostructured potassium-contained manganese oxides has been discussed in terms of influences of Li/Mn stoichiometry during molten___________________________________________________________________________ page 164 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS salt mixing, crystal phases and microstructure of precursory nanostructured MnO2. It is exhibited that α-MnO2 with suitable-sized one-dimensional tunnels in lattices facilitates the formation of chemical-level mixture of Li, Mn and O, and ensuring morphological retention after molten-salt lithiation. Compared to α-MnO2, the interlayer gap in δ-MnO2 crystal lattices is too large to ensure chemical-level mixture or morphology retention. It is suggested that the precursory Li/Mn ratio during molten-salt treatment should be prudently controlled, aiming to restraining excessive surface-absorption of Li and facilitating an effective Li/K exchange process. Also, one-dimensional nanoarchitectured precursory manganese oxide is advantageous over its nanoparticle counterparts on morphological retention after post-annealing process, due to its the enhanced stability against large local strains. Electrochemical measurements show that the prepared phase-pure and highly crystalline spinel-typed lithium manganese oxide nanorods in morphological replica of precursory α-MnO2 nanorods deliver a reversible specific capacity 94 mAh g−1 upon 200 times of charge–discharge cycling at a rate of 10 C. Lithium rich and deficient effects in LixCoPO4 (x = 0.90, 0.95, 1, 1.05) as cathode material for lithium-ion batteries Electrochimica Acta, 88, 15 January 2013, 865-870 Jiantie Xu, Shu-Lei Chou, Maxim Avdeev, Matthew Sale, Hua-Kun Liu, ShiXue Dou A series of LixCoPO4 (x = 0.90, 0.95, 1, 1.05) compounds with different lithium content in the starting compositions were prepared by the sol–gel method. The phase identification was carried out by X-ray diffraction and neutron diffraction. The structure, atom positions, and occupancies were characterized by neutron diffraction. The morphology of LixCoPO4 (x = 0.90, 0.95, 1, 1.05) was examined by field emission scanning electron microscopy. Electrochemical analysis indicated that Li0.95CoPO4 presented the highest discharge capacity at various current densities among all the different x value compounds. The Li0.95CoPO4 showed better cycling stability and coulombic efficiency in the room temperature ionic liquid electrolyte ([C3mpyr][NTf2] containing 1 M LiNTf2) at various current densities in the voltage range of 3.5–5.0 V than in the conventional electrolyte (1 M LiPF6 in ethylene carbonate:diethyl carbonate). Ionic liquid doped polybenzimidazole membranes for high temperature Proton Exchange Membrane fuel cell applications Journal of Power Sources, 222, 15 January 2013, 202-209 Erik van de Ven, Anisa Chairuna, Géraldine Merle, Sergio Pacheco Benito, Zandrie Borneman, Kitty Nijmeijer In this work we propose the use of the ionic liquid 1-H-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([h-mim] Ntf2) as conductive filler in a tailor-made porous, polymeric polybenzimidazole (PBI) support as proton ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 165 PUBLICATIONS conductive membrane for high temperature (>100 °C) fuel cell applications. PBI is chosen because of its excellent thermal and mechanical stability, while the choice for the ionic liquid is based on its high proton conductivity, low water sorption, thermal stability and low viscosity. The morphology of the porous PBI support is especially tailored for this application using a delayed immersion precipitation process. The macrovoid free porous structure has a porosity of 65% and a pore size of approximately 0.5 µm. Pores filling with ionic liquid by direct immersion of the PBI support into molten ionic liquid at 50 °C introduced the membrane proton conductivity. After impregnation the proton conductivity of this PBI/IL membrane reached a value of 1.86 mS cm−1 at 190 °C. Fuel cell performance of these membranes clearly exceeds that of Nafion 117 at temperatures above 90 °C. A power density of 0.039 W cm−2 is obtained at the intended operation temperature of 150 °C, which proofs that the developed PBI/IL membrane can be considered as a serious candidate for high temperature fuel cell applications. Densification of Sm0.2Ce0.8O1.9 with the addition of lithium oxide as sintering aid Journal of Power Sources, 222, 15 January 2013, 367-372 Shiru Le, Shengcai Zhu, Xiaodong Zhu, Kening Sun 20 mol% samarium doped cerium oxide (Sm0.2Ce0.8O1.9, SDC) has one of the highest ionic conductivities as electrolyte for solid oxide fuel cell in intermediate temperature, but is restricted to commercial application for its poor densification behavior. The addition of 2 mol% Li2O in the Sm0.2Ce0.8O1.9 (SDC2) improves its maximum shrinkage rate from 4.6 × 10−3 min−1–1.1 min−1 at a heating rate of 10 °C min−1. The relative density of SDC2 achieves 99.5% at 898 °C and 3 °C·min−1, while it is only 82% for SDC at 1250 °C and 3 °C min−1. The grain boundary diffusion is the densification mechanism, and the mobility of grain boundary increases from 9.8 × 10−19 m3 N−1 s−1 of SDC to 4.2 × 10−17 m3 N−1 s−1 of SDC2 at 900 °C. The activation energy for densification as high as 5.5 ± 0.5 eV for SDC2 contributes to the formation of liquid phase in the grain boundary. The open circuit voltage of the cell using SDC2 as electrolyte as high as 0.78 V at 600 °Cunder solid oxide fuel cell (SOFC) working conditions demonstrates its promising for SOFC electrolyte. On the incorporation of protic ionic liquids imbibed in large pore zeolites to polybenzimidazole membranes for high temperature proton exchange membrane fuel cells Journal of Power Sources, 222, 15 January 2013, 483-492 A. Eguizábal, J. Lemus, M.P. Pina Conducting fillers based on 2-hydromethyl) trimethylammoniun dimethyl phosphate (IL1), N,N-dimethyl-N-(2-hydroxyethyl) ammonium bis(trifluoromethanesulfonyl) imide (IL2) and 1-H-3-methylimidazolium ___________________________________________________________________________ page 166 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS bis(trifluoromethanesulfonyl)imide (IL3) encapsulated in large pore zeolites (NH4BEA and NaY) have been added to the PBI casting solution for the preparation of high temperature proton exchange membranes (HTPEMs). The filler loading has been systematically varied from 3% to 20% wt. for all the studied composites. The morphological, physicochemical, and electrochemical properties of the as prepared hybrid doped PBI membranes have been fully characterized. For a given conduction filler, the optimum loading is found to be 3% wt. as inferred from the conductivity measurements at 0.05 water molar fraction. Among the tested, the outstanding electrolyte membranes are those containing IL3-NaY. The exhibited through-plane proton conductivity is 54 mS cm−1 at 200 °C for the optimum PBI + IL3-NaY_3%wt hybrid membrane. The so obtained results are explained by the assisted 1-H-3methylimidazolium and bis(trifluoromethanesulfonyl) imide hydrogen bonding type interactions, clearly beneficial for the proton conduction processes. Moreover, the H2 permeability values for the hybrid electrolyte membranes and pure PBI are quite similar at the examined conditions; indicating the suitability of the preparation procedure in terms of fuel cross-over. The H+/H2 transport selectivity of the optimum IL3-NaY composite membrane clearly outperforms pure PBI and zeolite-PBI counterparts at 50°, 100° and 150 °C. Finally, the optimum composite membranes have been validated in H2/O2 single cell under non humidified conditions up to 180 °C as a “proof of concept” demonstration. Electrochemical reduction of iron oxide in molten sodium hydroxide based on a Ni0.94Si0.04Al0.02 metallic inert anode Electrochimica Acta, 87, 1 January 2013, 148-152 Shubo Wang, Jianbang Ge, Yuejiao Hu, Hongmin Zhu, Shuqiang Jiao Electrochemical tests, including anodic polarization, Tafel polarization and electrochemical impedance spectrum (EIS), were used to evaluate the anodic behaviors of a ternary alloy of Ni0.94Si0.04Al0.02 in molten NaOH at 773 K. The results revealed that a conductive passivation layer had formed during electrolysis, which protected the Ni0.94Si0.04Al0.02 substrate from further attacked. An in situ test of anodic gases using a mass spectra indicated that oxygen was emitted from the interface of the Ni0.94Si0.04Al0.02 anode. Meanwhile, the iron sponge can be electrochemically produced when Fe2O3 is used as cathode. The significant result is that the Ni0.94Si0.04Al0.02 alloy is promising as an inert anode in molten NaOH electrolyte for a green metallurgical process. Application of graphene–SnO2 nanocomposite modified electrode for the sensitive electrochemical detection of dopamine Electrochimica Acta, 87, 1 January 2013, 317-322 Wei Sun, Xiuzheng Wang, Yuhua Wang, Xiaomei Ju, Li Xu, Guangjiu Li, Zhenfan Sun ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 167 PUBLICATIONS In this paper a nanocomposite prepared by graphene (GR) and SnO2 nanosheets was used to modify a N-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode. The presence of GR–SnO2 nanocomposite on the electrode surface exhibited synergistic effects to improve the electrochemical performance of the modified electrode. Electrochemical behaviors of dopamine (DA) on the electrode were evaluated by cyclic voltammetry and differential pulse voltammetry. The results indicated that the GR–SnO2 nanocomposite modified electrode displayed high electrocatalytic activity to the oxidation of DA with the increase of the redox peak currents and the decrease of the peak-topeak separation. Under the selected conditions the oxidation peak current was proportional to the DA concentration in the range from 0.5 to 500.0 µmol/L with a detection limit of 0.13 µmol/L (S/N = 3). The modified electrode showed excellent selectivity and sensitivity even in the presence of high concentration of uric acid. The proposed method was applied to determine DA content in real samples with satisfactory results. Ultra fast electrochromic switching of nanostructured NiO films electrodeposited from choline chloride-based ionic liquid Electrochimica Acta, 87, 1 January 2013, 341-347 G.F. Cai, C.D. Gu, J. Zhang, P.C. Liu, X.L. Wang, Y.H. You, J.P. Tu Nanostructured nickel oxide (NiO) thin films were prepared by a simple electrodeposition in choline chloride-based ionic liquid followed by an oxidation in air. Uniform granules and some voids opened between these granules were presented in the polycrystalline NiO films deposited for 10 and 30 s, but the film became compact as the deposition time increased to 60 s. The optical transmittance of the film decreased with the increase of the film thickness. All the NiO films exhibit high coloration efficiency, fast electrochromic switching and good cycling durability. The ultra fast switching time (0.74 s and 0.88 s) and maximum coloration efficiency of 250 cm2 C−1 were observed for the film deposited for 10 s. Photovoltaic performance of bifacial dye sensitized solar cell using chemically healed binary ionic liquid electrolyte solidified with SiO2 nanoparticles Electrochimica Acta, 87, 1 January 2013, 425-431 Burak Cosar, Kerem Cagatay Icli, Halil Ibrahim Yavuz, Macit Ozenbas In this study, we investigated the effect of electrolyte composition, photoanode thickness, and the additions of GuSCN (guanidinium thiocyanate), NMB (Nmethylbenimidazole), and SiO2 on the photovoltaic performance of DSSCs (dye sensitized solar cells). A bifacial DSSC is realized and irradiated from front and rear sides. The devices give maximum photovoltaic efficiencies for 70% PMII (1-propyl-3-methyl-imidazolium iodide)/30% (EMIB(CN)4) (1-ethyl-3-methylimidazolium tetracyanoborate) electrolyte composition and 10 µm thick ___________________________________________________________________________ page 168 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS photoanode coating which is considered to be the ideal coating thickness for the diffusion length of electrolyte and dye absorption. A significant increase in the photocurrent for DSSCs with optimum molarity of 0.1 M GuSCN was observed due to decreased recombination which is believed to be surface passivation effect at photoanode electrolyte interface suppressing recombination rate. Moreover, optimum NMB molarity was found to be 0.4 for maximum efficiency. Addition of SiO2 to the electrolyte both as an overlayer and dispersed particles enhanced rear side illuminated cells where dispersed particles are found to be more efficient for the front side illuminated cells due to additional electron transport properties. Best rear side illuminated cell efficiency was 3.2% compared to front side illuminated cell efficiency of 4.2% which is a promising result for future rear side dye sensitized solar cell applications where front side illumination is not possible like tandem structures and for cells working from both front and rear side illuminations. Origin of the correlation between the standard Gibbs energies of ion transfer from water to a hydrophobic ionic liquid and to a molecular solvent Electrochimica Acta, 87, 1 January 2013, 591-598 Jan Langmaier, Stanislav Záliš, Zdeněk Samec, Viktor Bovtun, Martin Kempa Cyclic voltammetry was used to evaluate the standard Gibbs energy of transfer of a series of semi-hydrophobic ions from water to the newly synthesized highly hydrophobic ionic liquid (IL) composed of the tridodecylmethylammonium (TDMA+) cation and the dicarbollylcobaltate (DCC−) anion. Results were compared with those reported for the ion transfer to 1,2-dichloroethane (DCE) and to ILs composed of the same cation but a structurally different anion: tetrakis(pentafluorophenyl)borate (TPFPB−) or tetrakis[3,5bis(trifluoromethyl)phenyl]borate (TFPB−), and composed of the structurally different (ferrocenylmethyl)dodecyldimethylammonium+ cation (FcMDDA+) and the same anion (TFPB−). Dielectric relaxation spectroscopy (DRS) measurements of TDMADCC and TDMATPFPB provided the static (ɛs) and optical (ε∞) dielectric constants as the low- and high-frequency limits of the complex dielectric permittivity, respectively, as well as the corresponding relaxation times. The observed differences in the dielectric properties were clarified on the basis of the density functional theory (DFT) calculations of the ground state electronic structure, ion (ion radius) and dipole moment of the constituent IL ions. Contributions of the electrostatic and solvophobic interactions to the standard Gibbs energy of ion transfer were estimated using the advanced Born–Uhlig theory. The conclusion was made that the correlation established between the standard Gibbs energies of ion transfer from water to the studied ILs and to DCE has the origin in similar solvophobic contributions rather than in the comparable polarity of TDMADCC (ɛs = 11.7) and ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 169 PUBLICATIONS TDMATPFPB (ɛs = 7.1) and DCE (ɛs = 10.5), as characterized by the static dielectric constant ɛs. TiO2 flowers and spheres for ionic liquid electrolytes based dye-sensitized solar cells Electrochimica Acta, 87, 1 January 2013, 629-636 Liang Feng, Jianguang Jia, Yanyan Fang, Xiaowen Zhou, Yuan Lin Micro-sized 3D branched flower like and sphere TiO2 have been synthesized through a controlled hydrolysis followed by hydrothermal process. The resultant flower and sphere TiO2 were characterized by SEM, XRD, BET and light scattering measurements. Overwhelming anatase and strong light scattering were exhibited for the flower sample. Pure sphere and flower and sphere-mixed (flower/sphere) films were formed and applied as photoelectrodes for dyesensitized solar cells (DSCs) with both ionic liquid and gelled ionic liquid electrolytes. The devices exhibited considerably enhanced overall energy conversion efficiency in comparison with that of those derived from TiO2 nanoparticles. The superior performances were attributed to their fast electrolyte diffusion and good interfacial contact of TiO2/electrolyte as validated by EIS investigations as well as light scattering. The participation of flowers with the sphere films further improved the electrolyte penetration and light scattering, making the flower/sphere device the most efficient with a low dye loading. Discharge behaviour and interfacial properties of a magnesium battery incorporating trihexyl(tetradecyl)phosphonium based ionic liquid electrolytes Electrochimica Acta, 87, 1 January 2013, 701-708 Timothy Khoo, Anthony Somers, Angel A.J. Torriero, Douglas R. MacFarlane, Patrick C. Howlett, Maria Forsyth Magnesium-air batteries are a promising high-energy density power source that utilises an active magnesium electrode and oxygen. Herein, the magnesium surface formed during 0.2 mA/cm2 galvanostatic discharge in trihexy(tetradecyl)phosphonium chloride ionic liquid electrolyte was characterised using FTIR, XPS and mass spectroscopy and the complex nature of the interfacial film formed is described. This film has a conductive gel-like structure and consists of hydrated organophosphonium– magnesium(hydroxyl)chlorides. A laboratory synthesised form of the gel showed comparable discharge behaviour and was able to support a discharge current of 0.05 mA/cm2. The ionic liquid is shown to support oxygen reduction currents of greater than 0.8 mA/cm2, suggesting that this electrolyte is a suitable candidate for magnesium-air battery applications. Electrochemical study of copper chloride complexes in the RTIL 1-butyl-1methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ___________________________________________________________________________ page 170 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Electrochimica Acta, 87, 1 January 2013, 739-748 Tuomas Vainikka, David Lloyd, Lasse Murtomäki, José A. Manzanares, Kyösti Kontturi The electrochemistry of copper(I) and copper(II) chloride complexes in the RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, BMPTf2N, has been studied with constant current electrolysis and cyclic staircase voltammetry at temperatures between 21.0 and 96.0 °C and in different concentrations of chloride. The chloride concentration was controlled by addition of 1-butyl-1-methylpyrrolidinium chloride, BMPCl. An important finding is the evidence of a three-coordinated complex, Cu(I)Cl32− which has not been found in organic chloroaluminates without a significant increase in temperature. Two Cu(I) species were found at molar ratios of [Cl−]/[Cu] < 4. The kinetic parameters for the quasi-reversible Cu(I)–Cu(II) electron transfer were obtained with non-linear fitting. Successful fits required that the charge transfer coefficients for the reduction of Cu(II) (α) and oxidation of Cu(I) (β) did not sum up to unity, i.e. α + β ≠ 1. This result was interpreted using Tsallis nonextensive thermostatistics. Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butylN-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide solid polymer electrolytes for lithium batteries Electrochimica Acta, 87, 1 January 2013, 779-787 Morten Wetjen, Guk-Tae Kim, Mario Joost, Martin Winter, Stefano Passerini An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-strippingplating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160 mAh g−1 at high discharge rates (1 C) and temperatures above 60 °C. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 171 PUBLICATIONS Crosslinked gel polymer electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium ion battery applications Electrochimica Acta, 87, 1 January 2013, 889-894 Chen Liao, Xiao-Guang Sun, Sheng Dai Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY·TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY·TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY·TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g−1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g−1 by using a thinner membrane and cycling at 50 °C. Electrochemical fabrication of nanoporous gold-supported manganese oxide nanowires based on electrodeposition from eutectic urea/choline chloride ionic liquid Electrochimica Acta, 87, 1 January 2013, 918-924 Claudio Mele, Massimo Catalano, Antonietta Taurino, Benedetto Bozzini In this study an electrochemical approach is proposed for the fabrication of nanoporous gold (NPG)-supported manganese oxide nanowires. This method consists in: (i) electrodepositing an Au–Mn alloy, (ii) selectively corroding Mn under electrochemical control, forming simultaneously the NPG support and the functional Mn-oxide decorating the nanopores. The electrodeposition process is carried out from a bath based on eutectic urea/choline chloride ionic liquid. The electrochemical dealloying/oxidation step is performed in an aqueous solution. The oxidation process, performed by cyclic voltammetry (CV) in aqueous solution, has been monitored in situ by visible reflectivity measurements. The crystal structure and the morphology of the electrodeposited Au–Mn alloy have been examined by XRD and SEM, respectively. The 3D morphology of the nanostructure has been characterised by FIB/FEG-SEM. The specific capacity of NPG-supported nanostructured Mn-oxide has been measured by CV and found to be notably better than that of unsupported electrodeposited Mn-oxide nanowires. Prediction of salting-out and salting-in constants Journal of Molecular Liquids, 177, January 2013, 7-10 Yizhak Marcus ___________________________________________________________________________ page 172 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS An expression is established to predict the Setchenow salting constants of solid and liquid organic compounds from aqueous solutions by electrolytes. It employs the conventional standard partial molar volumes and the intrinsic molar volumes of the ions. It also uses properties for the non-electrolytes that are foreign to their aqueous solution behavior: their molar volumes and either the Kamlet/Taft polarity/polarizability indexes or the Hildebrand solubility parameters. The expression is tested on data not included in the correlations used to establish it. Protic pyridinium ionic liquid as a green and highly efficient catalyst for the synthesis of polyhydroquinoline derivatives via Hantzsch condensation in water Journal of Molecular Liquids, 177, January 2013, 44-48 Mahmood Tajbakhsh, Heshmatollah Alinezhad, Mohammad Norouzi, Saeed Baghery, Maryam Akbari The four-component Hantzsch condensation reaction of dimedone, ethyl acetoacetate, ammonium acetate and various aromatic and aliphatic aldehydes in the presence of 2-methylpyridinium trifluoromethanesulfonate ([2-MPyH]OTf) as a green and highly efficient catalyst in water affords polyhydroquinoline derivatives in good to excellent yields. This reaction has been carried out in the presence of 1 mol% of [2-MPyH]OTf at room temperature. The described novel synthesis method proposes several advantages of short reaction times, high yields, mild condition, high melting point, simplicity and easy workup compared to the traditional method of synthesis. Densities and viscosities of imidazolium and pyridinium chloroaluminate ionic liquids Journal of Molecular Liquids, 177, January 2013, 85-93 Wioletta Ochędzan-Siodłak, Katarzyna Dziubek, Dawid Siodłak The chloroaluminate ionic liquids are used in various types of reactions. However, due to their particular vulnerability on water, their physical properties have not been previously investigated very extensively. The densities and viscosities of series imidazolium and pyridinium chloroaluminate ionic liquids having alkyl (butyl, hexyl, octyl) or aralkyl (benzyl, ethylphenyl) chain at the cation, various effective molar fraction of AlCl3 (χAlCl3 = 0.5, 0.65, 0.7), as well as they mixture and mixture with common organic solvents (hexane, toluene) were measured at the temperature range 293.15–343.15 K (20–70 °C). Densities, and particularly viscosities decrease with the increase of temperature. The density decreases with the increase of the length of the alkyl chain. The type of cation also influences the density, however, the order is different than for nonhaloaluminate ionic liquids and depends on the alkyl chain length. Viscosity increases with increasing alkyl chain length, but it is not a linear trend. The ionic liquid with meta position of the alkyl chain is considerably more dense and more ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 173 PUBLICATIONS viscous than para isomer. The presence of aromatic phenyl ring at the side chain of the cation increases both density and viscosity. Higher effective molar fraction of AlCl3 increases density and decreases viscosity, however, for the imidazolium ionic liquid the change of viscosity diminishes at higher temperatures. Organic solvents decrease both density and viscosity of the ionic liquids, but aliphatic hexane imposes much smaller effect than aromatic toluene. The mixture of two ionic liquids has density and viscosity between those for constituents. This extends the application of the aralkyl ionic liquids over temperatures, in which they are in solid state. Hydrogen bonding investigation in 1-ethyl-3-methylimidazolium based ionic liquids from density functional theory and atoms-in-molecules methods Journal of Molecular Liquids, 177, January 2013, 94-101 Mohammad Reza Housaindokht, Hossein Eshtiagh Hosseini, Mohammad Sadegh Sadeghi Googheri, Hassan Monhemi, Reza Izadi Najafabadi, Narjes Ashraf, Mostafa Gholizadeh Because of special importance of hydrogen bond in the non-bonded interaction potential between two ionic liquid's parts is decided to investigate hydrogen bonding in these compounds. Two overviews are chosen to explain the hydrogen bonding in five different popular imidazolium based ionic liquids; EMI-TFSI, EMI-ES, EMI-Lactate, EMI-NO3 and EMI-PF6. Based on van der Waals atomic radii viewpoint, three types of hydrogen bond are determined in these ionic liquids that are CH…N, CH…O and CH…F respectively. Based on our results, the maximum number of hydrogen bond exists in EMI-PF6 while the strongest hydrogen bond is related to the EMI-Lactate ionic liquid. Electron density analysis of hydrogen bond critical points indicated that the type and position of hydrogen bond are in agreement with hydrogen bond length values. From this standpoint, the EMI-Lactate has the largest amount of bond critical points, 0.034 amu, while the EMI-PF6 has the maximum number of them. These observations are in agreement with van der Waals atomic radii viewpoint. In addition to hydrogen bond strength, the radius of the hydrogen bonding is also important in non-bonded interaction potential. For this purpose, distance dependence of bond critical point (ρBCP), as a measure of the strength of hydrogen bonds, is examined. Detailed analysis showed that ρBCP is an exponential decaying function of distance, as the hydrogen bond disappeared above 2.5 Å. It is consistent with van der Waals atomic radii standpoint. Finally polynomial inverse third order equation is obtained for non-bonded interaction potential as a function of intermolecular distance. Based on the outcomes, these potentials are long-range which leads to a dissociation distance above 8 Å in these ionic liquids. These finding non-bonded interaction potentials can be used as initial parameters for force filed definition. ___________________________________________________________________________ page 174 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ion-pairs formed in [Mim+][N(CN)2−] ionic liquid: Structures, binding energies, NMR SSCCs, volumetric, thermodynamic and topological properties Journal of Molecular Liquids, 177, January 2013, 119-128 Hossein Roohi, Shiva Khyrkhah The strong and directional H-bonds formed between cation and anion in methylimidazolium dicyanamide ionic liquid [Mim+][N(CN)2−] have been investigated using MP2, B3LYP, M052X and M062X methods in conjunction with the 6-311++G(2d,2p) basis set. With five preferential binding sites in the vicinity of the Mim+ ring, five ion pairs (A–E) were found on the potential energy surface. The binding energy, Gibbs free energy and enthalpy of formation, structural, volumetric (density, viscosity, conductivity and heat capacity) and topological properties as well as NMR one- and two bonds spin– spin coupling constants (SSCCs) were calculated. Ion pairs have electronic binding energies (BEs) in the range of − 78 to − 95 kcal/mol at MP2/6-311++G (2d,2p) level, − 73 to − 90 kcal/mol at B3LYP/6-311++G(2d,2p) level, − 77 to − 93 kcal/mol at M052X/6-311++G(2d,2p) level and − 78 to − 94 kcal/mol at M062X/6-311++G(2d,2p) level. The results show that the binding energy of ion pairs drastically diminishes with the polarity of solvent. The charge analysis was done using natural bond orbital (NBO) analysis. The nature of intermolecular interactions in the [Mim+][N(CN)2−] IL was characterized by Bader's quantum theory of atoms in molecules (QTAIM) method. Topological investigations of binary mixtures containing 1-ethyl-3methylimidazolium tetrafluoroborate and anilines Journal of Molecular Liquids, 177, January 2013, 133-144 V.K. Sharma, Subhash Solanki The densities, ρ, speeds of sound, u of 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + aniline or N-methylaniline or 2-methylaniline (j) binary mixtures at 293.15, 298.15, 303.15, and 308.15 K and excess molar enthalpies, HE of the same mixtures at 298.15 K have been measured over entire mole fraction using DSA-5000 and 2-Drop microcalorimeter respectively. Excess molar volumes, VE and excess isentropic compressibilities, κSE values have been predicted by utilizing the measured densities and speeds of sound data. The Graph theory which deals with the topology of the constituents of mixtures has been applied to predict (i) state of components of ionic liquid mixture in their pure and mixed state; (ii) nature and extent of interactions existing in mixtures; and (iii) VE, HE and κSE values. The analysis of VE data in terms of Graph theory suggests that while 1-ethyl-3-methylimidazolium tetrafluoroborate is characterized by electrostatic forces of attraction and exists as monomer; aniline or N-methylaniline or 2-methylaniline exists as associated molecular entities. Further, (i + j) mixtures are characterized by interactions between nitrogen and fluorine atoms of 1-ethyl-3-methylimidazolium tetrafluoroborate with nitrogen ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 175 PUBLICATIONS and hydrogen atoms of aniline or N-methylaniline or 2-methylaniline to form 1:1 molecular complex. The IR studies also support this view point. The VE, HE and κSE values predicted by Graph theory compare well with the experimental values. Mild basic ionic liquid catalyzed four component synthesis of functionalized benzo[a]pyrano[2,3-c]phenazine derivatives Journal of Molecular Liquids, 177, January 2013, 162-166 Hamid Reza Shaterian, Majid Mohammadnia An efficient, mild, and one-pot quantitative procedure for the preparation of functionalized benzo[a]pyrano[2,3-c]phenazine derivatives from four component reaction of 2-hydroxynaphthalene-1,4-dione, o-phenylenediamine, aldehydes, and malononitrile in the presence of basic ionic liquids such as 1butyl-3-methylimidazolium hydroxide, 3-hydroxypropanaminium acetate, pyrrolidinium formate, pyrrolidinium acetate, 1,8-diazabicyclo[5.4.0]-undec-7en-8-ium acetate, and piperidinium formate as the catalysts has been developed. The ionic liquid was stable during the reaction process and could also be reused several times with consistent activity. This procedure may be a practical alternative to the existing one reported procedure to meet the need of academe as well as industries. Water effect on physicochemical properties of 1-butyl-3-methylimidazolium based ionic liquids with inorganic anions Journal of Molecular Liquids, 177, January 2013, 267-272 E.P. Grishina, L.M. Ramenskaya, M.S. Gruzdev, O.V. Kraeva Room temperature ionic liquids of 1-butyl-3-methylimidazolium − tetrafluoroborate, [bmim][BF4], nitrate, [NO3] , phosphate, [PO4]3 −, and hydrogen sulfate, [HSO4]−, have been synthesized and characterized by 1HNMR, 13C-NMR, mass spectrometry and IR spectroscopy methods. The effect of nature of inorganic anion on hygroscopic property has been studied. Physicochemical properties such as density, viscosity, melting point, freezing point, glass transition, thermal decomposition temperature and specific electrical conductivity have been determined. The influence of temperature and water concentration on density, viscosity and specific electrical conductivity values has been investigated. The dependence of physicochemical properties against anion nature and water content has been explained according to cation–anion interactions. The anomalous behaviors of density or conductivity values for equimolecular aqueous solutions of 1-butyl-3-methylimidazolium hydrogen sulfate or tetrafluoroborate ionic liquids have been found and associated with significant restructuring. The formation of crystalline hydrates of the composition of [bmim][BF4]x0.5H2O was observed. ___________________________________________________________________________ page 176 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Volumetric properties of the ionic liquids: [C6mim][MeSO4], [C6mim][EtSO4], [C4mim][EtSO4] and their mixtures with methanol or ethanol Journal of Molecular Liquids, 177, January 2013, 301-305 Dobrochna Matkowska, Tadeusz Hofman Densities of pure ionic liquids, 1-hexyl-3-methylimidazolium methylsulfate [C6mim][MeSO4], 1-hexyl-3-methylimidazolium ethylsulfate, [C6mim][EtSO4], 1-butyl-3-methylimidazolium ethylsulfate [C4mim][EtSO4] and their mixtures with either methanol or ethanol, were measured at temperatures T/K = (283.15, 298.15, 313.15, 328.15) at ambient pressure. The excess volumes VE were correlated by the van Laar equation with the temperature-dependent parameters. Isobaric expansivity and excess isobaric expansivity were described as functions of temperature and composition. The negative deviations from ideal mixing were observed for excess VE and the excess isobaric expansivity αE. Effective preparation of 2-amino-3-cyano-4-aryl-5,10-dioxo-5,10-dihydro4H-benzo[g]chromene and hydroxyl naphthalene-1,4-dione derivatives under ambient and solvent-free conditions Journal of Molecular Liquids, 177, January 2013, 353-360 Hamid Reza Shaterian, Majid Mohammadnia The mild basic ionic liquids, 1,8-diazabicyclo[5.4.0]-undec-7-en-8-ium acetate, pyrrolidinium acetate, pyrrolidinium formate, piperidinium acetate, piperidinium formate, N-methylimidazolium formate, and 3-hydroxypropanaminium acetate catalyzed three-component synthesis of 2-amino-3-cyano-4-aryl-5,10-dioxo5,10-dihydro-4H-benzo[g]chromene and hydroxyl naphthalene-1,4-dione derivatives under ambient and solvent-free conditions. Simple procedure, high yields, short reaction time and environmentally benign method are advantages of these protocols. The inexpensive and non-toxic ionic liquids can be reused several times without noticeable loss of their activities. The mentioned ionic liquids show priority relative to other catalysts in the literature. Investigation on physical and electrochemical properties of three imidazolium based ionic liquids (1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-butyl-3-methylimidazolium methylsulfate) Journal of Molecular Liquids, 177, January 2013, 361-368 Ali Akbar Miran Beigi, Majid Abdouss, Maryam Yousefi, Seied Mahdi Pourmortazavi, Amir Vahid Three types of imidazolium based ionic liquids, 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([EMIM][NTf2]) and 1-butyl-3___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 177 PUBLICATIONS methylimidazolium methylsulfate ([BMIM][MeSO4]) were prepared and a variety of their fundamental properties such as kinematic (ν) and dynamic (η) viscosities, thermal stability, surface tension (σ ), refractive index (nD), pH and density (ρ) were investigated as a function of temperature. The coefficients of thermal expansion (αp) of the pure liquids were also calculated from the experimental values of the density at different temperatures. Electrochemical studies of these pure fluids as media were also studied at screen printed glassy carbon electrode (SP-GCE). The measurements were performed on a single drop of ionic liquids at surface of a screen-printed three electrode cell. The results showed an ideal wide range of potential windows for studies of electrochemical behavior of some species such as hydrogen sulfide and thiols in the lipophilic and hydrophilic ionic liquids. These properties were studied for special purposes such as development of electroanalytical methods for trace determination of organosulfur compounds in petroleum and its products. N-(2-hydroxyethyl)-ethylenediamine-based ionic liquids: Synthesis, structural characterization, thermal, dielectric and catalytic properties Journal of Molecular Liquids, 177, January 2013, 369-375 Ahmet Karadağ, Ali Destegül Three novel acetate and formate ammonium salts of N-(2-hydroxyethyl)ethylenediamine (Hydeten) were synthesized as room temperature ionic liquids (RTILs) {2-(2-hydroxy ethylamino)-ethanaminium formate (IL1a), 2-amino-N(2-hydroxyethyl)-ethanaminium formate (IL1b), and 2-(2-hydroxyethylamino)ethanaminium acetate (IL2)}. Their structures were characterized by using elemental analysis, FT-IR, 1H and 13C NMR techniques. Some thermal properties of these ILs were determined by using TG and DSC techniques. Real dielectric (ε′)-frequency (ω), imaginary dielectric (ε″)-frequency (ω), and conductivity (σAC)-frequency (ω) relationships of IL1a–b, IL2, and doped IL1–2 were investigated. These ILs were also tested as solvent or catalyst in the synthesis of some organic compounds. 1,3-Disulfonic acid imidazolium hydrogen sulfate as an efficient and reusable ionic liquid catalyst for the N-Boc protection of amines Journal of Molecular Liquids, 177, January 2013, 386-393 Farhad Shirini, Nader Ghaffari Khaligh 1,3-Disulfonic acid imidazolium hydrogen sulfate is easily prepared and used as an efficient and recyclable ionic liquid for the N-Boc protection of amines at room temperature and neat conditions. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be reused and recovered for several times without loss of activity. Enhancement in the thermal stability of the mesophases of 4-n-(decyloxy) benzoic acid due to Li ion beam irradiation ___________________________________________________________________________ page 178 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Journal of Molecular Liquids, 177, January 2013, 409-415 Rohit Liquid crystalline compound 4-n-(decyloxy) benzoic acid has been irradiated by Li ion beam in its crystalline phase at room temperature by a pelletron beam using 3 nA current. Thermodynamic, dielectric and UV–Visible spectroscopic characterization of the pure and irradiated materials has been carried out. Thermodynamical studies of the pure and irradiated materials show that all the transition temperatures, enthalpies and hence entropies are increased due to the irradiation suggesting enhancement in the thermal stability of the mesophases. Dielectric results obtained on the irradiated vis-à-vis pure material suggest how the value of the transverse component of the dielectric permittivity of the irradiated material increases in the SmC phase whereas it decreases in the N phase as compared to that of the pure material. UV–Visible spectrum of the irradiated material shows an additional peak along with the peak of the pure material suggesting formation of new species in the irradiated materials. A new ionic liquid organic redox electrolyte for high-efficiency iodine-free dye-sensitized solar cells Journal of Power Sources, 221, 1 January 2013, 328-333 Hongwei Wu, Zhibin Lv, Shaocong Hou, Xin Cai, Dan Wang, Hany Kafafy, Yongping Fu, Chao Zhang, Zengze Chu, Dechun Zou A new ionic liquid (IL) 5-mercapto-1-methyltetrazole 1-methyl-3propylimidazolium salt PMIT with di-5-(1-methyltetrazole) disulfide (T2) as the organic redox couple is adopted for application in IL dye-sensitized solar cells (DSSCs). Adopting ultralow-cost and superior catalytic ink carbon as the counter electrode (CE), the N719- and D102-sensitized devices show high efficiencies of 4.30% and 3.83% under 100 mW cm−2 light illumination, respectively. Electrochemical studies provide insights on the mass-transfer and recombination kinetics of the electrolyte and electrochemical catalysis of the CE. The ink carbon CE exhibits more excellent catalytic activity than the Pt CE for the redox couple. These show an attractive prospect of carbon materials for application in DSSCs based on new iodine-free ionic liquid organic electrolyte. Natural, cheap and environmentally friendly binder for supercapacitors Journal of Power Sources, 221, 1 January 2013, 14-20 N. Böckenfeld, S.S. Jeong, M. Winter, S. Passerini, A. Balducci In this work we report the use of natural cellulose as the binder for composite electrodes for electrochemical double-layer capacitors (EDLCs). Composite electrodes containing natural cellulose as the binder can be prepared using either ionic liquid based slurries or aqueous suspensions containing a polymeric stabilizer and a surfactant. These composite electrodes display good mechanical stability, uniform morphology and a thermal stability comparable to those made ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 179 PUBLICATIONS with conventional binders. Moreover, when used as electrodes in EDLCs, they allow the realization of devices able to display high performance in term of specific capacitance and cycling stability in all type of electrolytes used in EDLCs. Considering the appealing properties of natural cellulose, the introduction of this material as a binder in EDLCs could be an important contribution for the development of cheap, safe and environmentally friendly EDLCs. The TbBr3–LiBr binary system: Experimental thermodynamic investigation and assessment of phase diagram The Journal of Chemical Thermodynamics, 56, January 2013, 15-20 L. Rycerz, W. Gong, M. Gaune-Escard DSC was used to study the phase equilibrium in the TbBr3–LiBr binary system. The results obtained provided a basis for constructing the phase diagram of this system. It exhibits two compounds: Li5TbBr8, which decomposes in the solid state at 611 K, and Li3TbBr6, which melts congruently at 785 K with the related enthalpy 59.1 kJ·mol−1. The binary LiBr–TbBr3 system was then optimized using the available experimental information on phase diagram and thermodynamic properties. A two-sub-lattice ionic solution model (Li+)P:(Br−, TbBr6−3, TbBr3)Q was adopted to describe the liquid phase. The present assessment of the binary LiBr–TbBr3 system was in good agreement with the corresponding experimental data and confirmed their consistency. Topological investigations of binary mixtures containing ionic liquid 1ethyl-3-methylimidazolium tetrafluoroborate and pyridine or isomeric picolines The Journal of Chemical Thermodynamics, 56, January 2013, 123-135 Subhash Solanki, Neeti Hooda, V.K. Sharma The densities, ρ, speeds of sound, u of {1-ethyl-3-methylimidazolium tetrafluoroborate (i) + pyridine or α- or β- or γ-picoline (j)} at T/K = (293.15, 298.15, 303.15, and 308.15) and excess molar enthalpies, HE of the same set of mixtures at T/K = (298.15) have been measured over entire mole fraction range using DSA-5000 and 2-drop microcalorimeter. Excess molar volumes, VE and excess isentropic compressibilities, values have been predicted by utilizing the measured densities and speeds of sound data. It has been observed that VE, HE, and values for the studied mixtures are negative over entire composition. The connectivity parameter of third degree of a molecule, 3ξ (which in turn depends upon its topology) have been applied to predict (i) state of components of ionic liquid mixtures in their pure and mixed state; (ii) nature and extent of interactions existing in mixtures; and (iii) VE, HE, and values. The analysis of VE data in terms of Graph theory (which deals with topology of a molecule) suggest that while 1-ethyl-3-methylimidazolium tetrafluoroborate is characterised by electrostatic forces of attraction and exist as monomer; α- or β- or γ-picoline ___________________________________________________________________________ page 180 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS exist as associated molecular entities. Further, (i + j) mixtures are characterized by interactions between nitrogen and florine atoms of 1-ethyl-3methylimidazolium tetrafluoroborate with nitrogen and carbon atoms of pyridine or isomeric picolines to form 1:1 molecular complex. The IR studies also support to this view point. The VE, HE, and values predicted by Graph theory compare well with experimental values. Synthesis, physical, and thermodynamic properties of 1-alkylcyanopyridinium bis{(trifluoromethyl)sulfonyl}imide ionic liquids The Journal of Chemical Thermodynamics, 56, January 2013, 153-161 Urszula Domańska, Katarzyna Skiba, Maciej Zawadzki, Kamil Paduszyński, Marek Królikowski Synthesis of new ionic liquids (ILs) viz. 1-butyl-3-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [BCN3Py][NTf2], 1-hexyl-33 cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [HCN Py][NTf2], 1hexyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, 4 [HCN Py][NTf2], and 1-octyl-3-cyanopyridinium 3 bis{(trifluoromethyl)sulfonyl}imide, [OCN Py][NTf2] were performed. The specific basic characterization of new compounds by NMR spectra, elementary analysis, water content and glass transition temperature as well as melting temperature, enthalpy of fusion and decomposition of compounds TG/DTA determined by the differential scanning calorimetry, DSC is presented. The heat capacity was measured at three temperatures (298.15, 323.15, and 353.15) K and at pressure 0.1 MPa. The effect of temperature on the density and viscosity is reported over the temperature range from (293.15 to 363.15) K and at 0.1 MPa. The density and viscosity correlation for these systems was provided by an empirical polynomial. From the density–temperature dependence, the isothermal expansion coefficient (expansivity), α, was calculated. The surface tension of pure ionic liquids was measured at 0.1 MPa at five temperatures (298.15, 308.15, 318.15, 328.15, and 338.15) K. The surface thermodynamic functions such as surface entropy and enthalpy, critical temperatures according to the Eötvös and Guggenheim definition and the total surface energy of the ILs studied were derived from the temperature dependence of the surface tension values. The parachor and speed of sound for pure ionic liquids were described within a range of temperature from (298.15 to 338.15) K. A qualitative analysis on these quantities in terms of molecular interactions is reported. Evaluation of molecularly imprinted anion-functionalized poly(ionic liquid)s by multi-phase dispersive extraction of flavonoids from plant Journal of Chromatography B, Volumes 913–914, 15 January 2013, 61-68 Wentao Bi, Minglei Tian, Kyung Ho Row Molecularly imprinted anion-functionalized poly(ionic liquid)s (MAPILs) were prepared by radical polymerization for the multi-phase dispersive extraction ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 181 PUBLICATIONS (MPDE) of flavonoids from plants. Poly(ionic liquid)s were functionalized with different anions via anion metathesis to enhance their separation efficiency, called anion-functionalized poly(ionic liquid)s (APILs). A molecularly imprinting technique was introduced to produce specific recognition sites by forming complexes between the template molecules and anion-functionalized ionic liquid monomers to reduce the interactions with the interference substances and increase the selectivity. Multi-phase dispersive extraction (MPDE) was applied for separation instead of the traditional solid phase extraction method. The target compounds were first extracted by three-phase (sample–solvent–sorbent) dispersive extraction and cleaned up after removing the sample matrix. This method significantly decrease in the interference and analysis cost. A suitable sorbent for MPDE could be identified based on the adsorption behaviors of flavonoids on different MAPILs. The mean recovery yields of quercitrin, myricetin, and amentoflavone from Chamaecyparis obtusa under the optimized conditions were 88.07, 93.59, and 95.13%. This is a promising method for the extraction, separation and determination of flavonoids or other polyphenolic compounds from natural and other sources. Characterization of the Solutol® HS15/water phase diagram and the impact of the Δ9-tetrahydrocannabinol solubilization Journal of Colloid and Interface Science, 390, Issue 1, 15 January 2013, 129136 Sergio Murgia, Paolo Fadda, Giuseppe Colafemmina, Ruggero Angelico, Luigi Corrado, Paolo Lazzari, Maura Monduzzi, Gerardo Palazzo Here, the phase behavior of the commercial non-ionic surfactant Solutol® HS15 in water was investigated. The focus was on the evolution of the system nanostructure at low water content. Particularly, it was demonstrated that spherical micelles found in dilute surfactant solutions coalesce at a surfactant fraction close to 0.5. As consequence, a heterogeneous pseudo-binary mixture occurs. No liquid crystalline phases were detected even at the highest HS15 concentrations in water. Alteration of the micellar morphology induced by the addition of Δ9-tetrahydrocannabinol to the surfactant/water binary system was also investigated. It was found that the cannabinoid molecules become entrapped within the surfactant hydrophobic tails, thus increasing the surfactant effective packing parameter and inducing a radical change of the micelle shape. At sufficiently low water content (18–35 wt.%), such alteration of the interfacial packing results in a lamellar organization of the surfactant molecules. Influence of temperature on the electrochemical characteristics of Bi(1 1 1)|ionic liquid interface Journal of Electroanalytical Chemistry, 689, 15 January 2013, 51-56 Liis Siinor, Rauno Arendi, Karmen Lust, Enn Lust ___________________________________________________________________________ page 182 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS The electrochemical characteristics for electrochemically polished Bi(1 1 1) electrode in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) and 1butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) within temperature range from 298 K to 348 K were studied using electrochemical impedance spectroscopy and cyclic voltammetry. The region of ideal polarizability, series capacitance (Cs), double layer capacitance, adsorption capacitance, diffusion resistance and charge transfer resistance have been calculated and analyzed. Cs values were calculated from experimental Nyquist plots at constant ac frequencies and Cs depends on the composition of ionic liquid, electrode potential and ac frequency. However noticeable dependence of Cs on temperature can be seen only within the low ac frequency range from 1 Hz to 0.1 Hz. Based on the fitting results of impedance data, the restructuring of electrical double layer and adsorption of large organic ions is a kinetically slow process. Reduction mechanism and carbon content investigation for electrolytic production of iron from solid Fe2O3 in molten K2CO3–Na2CO3 using an inert anode Journal of Electroanalytical Chemistry, 689, 15 January 2013, 109-116 Diyong Tang, Huayi Yin, Wei Xiao, Hua Zhu, Xuhui Mao, Dihua Wang Iron and oxygen was recently electrochemically prepared in molten Na2CO3– K2CO3 eutectic melt at 750 °C using a solid iron oxide pellet cathode and a cheap Ni10Cu11Fe alloy inert anode. This paper focuses to reveal the detailed reduction kinetics of solid Fe2O3 in the melt and also the effect of reduction potential on the carbon content in the iron product. The reduction mechanism was systematically investigated by cyclic voltammetric measurements, potentiostatic electrolysis combining with the composition and morphology analysis of the products obtained at different potentials. It was found that the reduction of Fe2O3 involves three steps, with the formation of intermediate products, viz., NaFe2O3 and NaFeO2. The influence of electrolysis voltage/potential on the carbon content in the products was investigated by using both constant voltage and potentiostatic electrolysis under different conditions. The carbon content was found to be in the range of 0.035–0.76 wt.%, depending on the applied cathodic potential. The iron-based products with higher carbon content can be obtained upon electrolysis at a higher cell voltage or a more negative potential. The present results also demonstrated a controllable extraction of Fe–C steels with desired carbon content through an environmental friendly way. Determination of free metal ion concentrations with AGNES in low ionic strength media Journal of Electroanalytical Chemistry, 689, 15 January 2013, 276-283 D. Aguilar, C. Parat, J. Galceran, E. Companys, J. Puy, L. Authier, M. PotinGautier ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 183 PUBLICATIONS The determination of free metal ion concentrations of heavy metals, like Zn2+ or Cd2+, with AGNES (Absence of Gradients and Nernstian Equilibrium Stripping) requires an adequate selection of parameters such as deposition potential (linked to the gain, [M0]/[M2+]) and deposition time. In systems with low ionic strength, the peak potential of the Differential Pulse Polarogram (DPP) measured with low supporting electrolyte is not always suitable for the computation of the gain with existing expressions. The application of AGNES with a constant potential (regardless of the ionic strength) provides a direct measurement of the metal ion activity. When working with low ionic strength solutions, the selection of appropriate instrumentation is important to avoid changes in liquid junction potentials or leakages from the employed electrodes. The deposition times (for a given gain) have not been found to be greatly affected by the probed ionic strengths when working with just metal. A new strategy for the practical implementation of AGNES to measure free metal ion concentrations in samples with low KNO3 or Ca(NO3)2 concentrations consists in the computation of the deposition potential (to reach a certain gain) from the DPP peak potential at a sufficiently high ionic strength using a new expression. A speciation experiment with Zn2+ and glycine at pHs between 4 and 7.5, where [KNO3] = 0.001 M, shows that this methodology works well and also proves that it is possible to perform AGNES in systems with very low ionic strength. Removal of 1-ethyl-3-methylimidazolium cations with bacterial biosorbents from aqueous media Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 130-134 Sung Wook Won, Sun Beom Choi, Juan Mao, Yeoung-Sang Yun This study aims to determine whether biosorption can be used for the removal of ionic liquids (ILs), especially their cationic parts, from aqueous media. As a model IL, 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) was used. Five types of bacterial biosorbents were prepared from fermentation wastes through chemical modification of the bacterial surface. Screening study was performed to compare the cationic [EMIM] biosorption capacity among the bacterial biosorbents, indicating that the succinated Escherichia coli biomass (SB-E) was the best biosorbent for removing [EMIM] cations. The [EMIM] biosorption performance of SB-E was evaluated in detail through various experiments. The optimal pH range for [EMIM] biosorption was from 7 to 10, and biosorption equilibrium was reached within 10 min. The maximum uptake of SB-E was also estimated to be 72.6 mg/g. Moreover, [EMIM] cations were easily desorbed from [EMIM]-sorbed SB-E by adding acetic acid. Hydrolysis of polycarbonate catalyzed by ionic liquid [Bmim][Ac] Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 204-208 Xiuyan Song, Fusheng Liu, Lei Li, Xuequn Yang, Shitao Yu, Xiaoping Ge ___________________________________________________________________________ page 184 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Hydrolysis of polycarbonate (PC) was studied using ionic liquid 1-butyl-3methylimidazolium acetate ([Bmim][Ac]) as a catalyst. The influences of temperature, time, water dosage and [Bmim][Ac] dosage on the hydrolysis reaction were examined. Under the conditions of temperature 140 °C, reaction time 3.0 h, m([Bmim][Ac]):m(PC) = 1.5:1 and m(H2O):m(PC) = 0.35:1, the conversion of PC was nearly 100% and the yield of bisphenol A (BPA) was over 96%. The ionic liquid could be reused up to 6 times without apparent decrease in the conversion of PC and yield of BPA. The kinetics of the reaction was also investigated. The results showed that the hydrolysis of PC in [Bmim][Ac] was a first-order kinetic reaction with an activation energy of 228 kJ/mol. Sensitive determination of thallium species in drinking and natural water by ionic liquid-assisted ion-pairing liquid–liquid microextraction and inductively coupled plasma mass spectrometry Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 380-386 Leticia B. Escudero, Rodolfo G. Wuilloud, Roberto A. Olsina A fast and simple method involving separation and determination of thallium (Tl) species, based on novel ionic liquid-assisted ion pairing dispersive liquid– liquid microextraction (DLLME) method, was developed. Initially, Tl(III) was selectively complexed with chloride ion to form [TlCl4]− chlorocomplex. Subsequently, tetradecyl(trihexyl)phosphonium chloride ionic liquid ® − (CYPHOS IL 101) was used to form the ion-pair with [TlCl4] anion followed by extraction. The DLLME procedure was developed by dispersing 80 µL of carbon tetrachloride with 100 µL of ethanol added to the aqueous solution. After DLLME, the upper aqueous phase containing Tl(I) only was removed and analysed by inductively coupled plasma-mass spectrometry (ICP-MS). In contrast to Tl(III), Tl(I) species does not form neither stable nor anionic complexes with chloride ions and it was not extracted into the organic phase. Total Tl concentration was obtained by direct introduction of sample into ICPMS instrument. The calibration graph for the analyte was linear with a correlation coefficient of 0.9989. Under optimal conditions, detection limit of Tl species was 0.4 ng L−1. The relative standard deviation (n = 10) at 1 ng mL−1 Tl concentration level was 1.3% for Tl(I) and 1.5% for Tl(III). The method was successfully applied for fast speciation analysis of Tl at ultratrace levels in real water samples. A novel oxidative method for the absorption of Hg0 from flue gas of coal fired power plants using task specific ionic liquid scrubber Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 495-500 Zach Barnea, Tatyana Sachs, Mandan Chidambaram, Yoel Sasson A simple continuous process is described for the removal of mercury from gas streams (such as flue gas of a coal fired power stations) using imidazolium based Task Specific Ionic Liquids [TSILs] with the general structure ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 185 PUBLICATIONS ([RMIM][XI2−]) where X = Cl, Br or I. The latter are formed by blending dialkylimidazolium halide salts with iodine. When applied in a gas/liquid scrubber, these salts were shown to absorb >99% of elemental mercury originally present in a gas stream in concentration of 75–400 ppb. The mercury abatement is attained by oxidating the mercury to HgI2 which is bound as a stable IL complex ([RMIM+][XHgI2−]. The novel absorption system exhibits a remarkable mercury concentration factor of seven orders of magnitude. The final solution obtained contains up to 50% (w/w) mercury in the IL. Upon exposure to sodium formate, directly added to the saturated IL at 45 °C, reduced metallic mercury swiftly precipitated from the solution and could be quantitatively separated and collected. The free IL could be fully recycled. Automated carboxylesterase assay for the evaluation of ionic liquids’ human toxicity Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 563-569 Edite Cunha, Paula C.A.G. Pinto, José P.S. Carvalho, M. Lúcia M.F.S. Saraiva Aiming the prediction of ionic liquids’ (ILs) human toxicity, an automated carboxylesterase activity assay was developed. The method was implemented on a sequential injection analysis (SIA) system and relied on the hydrolysis of 4methylumbelliferyl acetate by the enzyme, to produce the fluorescent compound 4-methylumbelliferone (λexc = 365 nm; λem = 460 nm). The adopted approach was based on activity/inhibition assays in which the reduction of enzyme activity was denoted by a decrease of fluorescence. The activity assays were performed in aqueous media and in the presence of increasing concentrations of seven commercially available ILs and sodium bis(p-nitrophenyl) phosphate, a strong inhibitor of carboxylesterase. The inhibitory effects were quantified by means of the calculation of half maximal inhibitory effective concentration (EC50) values that were between 38 and 134 µmol L−1. This allowed us to perform some considerations about the toxicity of the compounds. The less and more toxic ILs found in this study were emim [Ms] and tbph [Ms], respectively. The developed SIA methodology is robust and exhibits good repeatability in all the tested conditions (rsd < 5.0%, n = 10). At the same time a reduction of costs was attained by reduced consumption of reagents and minimal effluent production (2 mL per cycle). A novel process for recovery of iron, titanium, and vanadium from titanomagnetite concentrates: NaOH molten salt roasting and water leaching processes Journal of Hazardous Materials, Volumes 244–245, 15 January 2013, 588-595 Desheng Chen, Longsheng Zhao, Yahui Liu, Tao Qi, Jianchong Wang, Lina Wang ___________________________________________________________________________ page 186 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A novel process for recovering iron, titanium, and vanadium from titanomagnetite concentrates has been developed. In the present paper, the treatment of rich titanium–vanadium slag by NaOH molten salt roasting and water leaching processes is investigated. In the NaOH molten salt roasting process, the metallic iron is oxidized into ferriferous oxide, MgTi2O5 is converted to NaCl-type structure of Na2TiO3, and M3O5 (M = Ti, Mg, Fe) is converted to α-NaFeO2-type structure of NaMO2, respectively. Roasting temperature and NaOH–slag mass ratio played a considerable role in the conversion of titanium in the rich titanium–vanadium slag during the NaOH molten salt roasting process. Roasting at 500 °C for 60 min and a 1:1 NaOH– slag mass ratio produces 96.3% titanium conversion. In the water leaching process, the Na+ was exchanged with H+, Na2TiO3 is converted to undefined structure of H2TiO3, and NaMO2 is converted to α-NaFeO2-type structure of HMO2. Under the optimal conditions, 87.3% of the sodium, 42.3% of the silicon, 43.2% of the aluminum, 22.8% of the manganese, and 96.6% of the vanadium are leached out. Preparation and characterization of PVDF/TiO2 hybrid membranes with ionic liquid modified nano-TiO2 particles Journal of Membrane Science, 427, 15 January 2013, 259-269 Fengmei Shi, Yuxin Ma, Jun Ma, Panpan Wang, Weixiao Sun PVDF/TiO2 hybrid microfiltration membranes with different contents of ionic liquid modified nano-TiO2 (IL-TiO2) were prepared via thermally induced phase separation (TIPS) method. The morphology of membranes was studied by scanning electron microscope. The TiO2 stability in the hybrid membranes was evaluated by XPS. The membrane properties such as pure water flux, porosity, pore size distribution and antifouling properties were also determined. Results showed that PVDF and PVDF/TiO2 hybrid membranes were formed by solid– liquid phase separation and had spherical crystallites structure with cells. The addition of IL-TiO2 particles to the PVDF/DMP mixtures had a strong effect on the crystallization temperature of hybrid membranes and crystallization formation in the TIPS process. Pure water flux and porosity first increased, and then decreased with the increase of IL-TiO2 content. Membranes with lower ILTiO2 content had a relatively higher TiO2 stability. The antifouling property of hybrid membranes was improved by the addition of IL-TiO2. Hopefully, the demonstrated method of nanoparticles synthesis and membrane preparation was favorable to fabricate catalytic hybrid membranes and antifouling membranes for water treatment. Electrospun PET supported-ionic liquid-stabilized CdS catalyst for the photodegradation of Rhodamine B under visible light Materials Letters, 91, 15 January 2013, 96-99 Herdeline Ann M. Ardoña, Fiona U. Paredes, Ian Harvey J. Arellano, Susan D. Arco ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 187 PUBLICATIONS We report the first synthesis of cadmium sulfide (CdS) nanowhiskers prepared by the sonochemical precipitation method using the green ionic liquid (IL), 1octyl-3-methylimidazolium lauryl sulfate, [OMIM]LS. The synthesized ILstabilized CdS was immobilized in polyethylene terephthalate (PET) fibers. The PET microfibers used as a support were produced via electrospinning of viscous PET solution. The whiskers assemble in an urchin-like crystal habit and exhibit a band-edge emission due to exciton recombination at 453.7 nm and a trap state emission due to surface defects at 648.1 nm. The catalyst/polymer ensemble was tested for its photocatalytic activity in the degradation of a model dye, Rhodamine B under visible light. The degradation rate of polymer-supported CdS catalyst is twice compared with the efficiency of the unsupported material. Synthesis and formation mechanism of cubic boron nitride nanorods in lithium bromide molten salt Materials Letters, 91, 15 January 2013, 206-208 Mingtao Zheng, Yingliang Liu, Peng Wang, Yong Xiao Cubic boron nitride nanorods (cBNNRs) were synthesized through a simple reaction between boron tribromide and sodium amide in lithium bromide molten salt medium at 600 °C in a sealed autoclave system. The cBNNRs observed by transmission electron microscopy have various diameters ranging from 8 to 25 nm with aspect ratios of about 10–20. X-ray diffraction and selected area electron diffraction pattern revealed the cubic phase of cBNNRs with a lattice constant a=3.625 Å. The B:N ratio obtained by energy dispersive X-ray spectroscopy was 1:1.12, and Fourier transform infrared spectrum showed a characteristic absorption at 1106 cm–1. The possible formation mechanism of cBNNRs in molten salt medium is also discussed. Fabrication of porous and interconnected PBI/P84 membranes using [EMIM]OAc as the green solvent Chemical Engineering Science, 87, 14 January 2013, 194-203 Ding Yu Xing, Sui Yung Chan, Tai-Shung Chung ultrafiltration In this study, we aimed to design PBI (poly-2,2′-(m-phenylene)-5,5′bibenzimidazole) blend membranes with a higher water flux by using a less amount of the expensive PBI material and by employing environmentally friendly ionic liquids as the solvent. Five commercially available polyimides and polyimide–amides were screened and P84 (BTDA-TDI/MDI, co-polyimide of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride and 80% methylphenylenediamine +20% methylenediamine) was chosen to blend with PBI because it formed miscible blends with PBI and interacted closely with the ionic liquid of 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc). An interesting interconnected network of the PBI/P84/[EMIM]OAc solution was evolved based on the highly charge-ordered characteristics of [EMIM]OAc. The ___________________________________________________________________________ page 188 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS blend solution displayed unusual rheological behavior: an initial shear thinning behavior under low shear rates followed by a Newtonian plateau. The incorporation of P84 in the blend system not only lowered the overall viscosity for easier membrane fabrication but also retarded the phase inversion process favorably to form a macrovoid-free morphology. PBI/P84 blend membranes were therefore fabricated for ultrafiltation via non-solvent induced phase inversion method. The effects of PBI/P84 composition and casting temperature on membrane morphology and separation performance were studied according to their phase inversion mechanisms. Compared to plain PBI ultrafiltration membranes, the newly developed PBI/P84 blend membranes exhibit an open cell structure and a reduced thickness which leads to a 50% higher pure water permeability and a larger pore diameter. The performance of ionic liquids and their mixtures in inhibiting methane hydrate formation Chemical Engineering Science, 87, 14 January 2013, 270-276 Anthony R. Richard, Hertanto Adidharma The performance of 1-ethyl-3-methylimidazolium chloride (EMIM-Cl), one of novel ionic liquid inhibitors for gas hydrate, in inhibiting methane hydrate at low and high ionic liquid concentrations is investigated in a pressure range of 10–20 MPa. Experiments on methane hydrate dissociation conditions in the presence of mixed ionic liquid and conventional inhibitors, such as sodium chloride (NaCl) and monoethylene glycol (MEG), as well as a mixture containing two ionic liquids, EMIM-Cl and 1-ethyl-3-methylimidazolium bromide (EMIM-Br), are also performed to investigate any possible synergistic effects. It is observed that single component solutions of EMIM-Cl demonstrate a progressive increase in inhibition effect with increasing concentration, which may surpass the effectiveness of MEG at high concentrations. Although the thermodynamic inhibition performance of the mixtures of EMIM-Cl and MEG does not show any synergistic effects at low pressures, it does at higher pressures. The mixture of EMIM-Cl and EMIM-Br also shows a synergistic effect at higher pressures. Unlike MEG or NaCl, inhibitors containing EMIM-Cl or EMIM-Br demonstrate an increase in inhibition effectiveness as pressure increases. Electrophilic fluorocyclization of unsaturated alcohols in ionic liquids Tetrahedron, 69, Issue 2, 14 January 2013, 833-838 Lyudmila F. Lourie, Yurii A. Serguchev, Maxim V. Ponomarenko, Eduard B. Rusanov, Michail V. Vovk, Nikolai V. Ignat'ev Fluorocyclization of phenyl-substituted alkenols in ionic liquids under action of N–F reagents namely F-TEDA-BF4 and N-fluorobenzenesulfonimide has been studied. Opposite to the non-stereoselective reaction in organic solvents the reaction in ionic liquids resulted in the formation preferably of the trans___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 189 PUBLICATIONS diastereomeric fluorinated cyclic ethers. 2-Difluoromethyl-2-phenyltetrahydrofuran was obtained by interaction of 4-phenylpent-4-en-1-ol with FTEDA-BF4 in ionic liquids. Ionic liquids as solvents for in situ dispersive liquid–liquid microextraction of DNA Journal of Chromatography A, 1272, 11 January 2013, 8-14 Tianhao Li, Manishkumar D. Joshi, Donald R. Ronning, Jared L. Anderson Six ionic liquids (ILs) were applied for the first time as solvents in the extraction and preconcentration of deoxyribonucleic acid (DNA) using an in situ dispersive liquid–liquid microextraction (DLLME) approach. The effect of different IL substituents and functional group on the extraction efficiency of DNA was investigated. The highest extraction efficiencies of DNA were obtained using 1(1,2-dihydroxypropyl)-3-hexadecylimidazolium bromide (C16POHIM-Br) and N,N-didecyl-N-methyl-d-glucaminium bromide [(C10)2NMDG-Br]. Extraction efficiencies higher than 97% were obtained using small amounts of IL (0.50 mg) for each extraction. The extraction of DNA from a sample matrix containing metal ions and protein revealed that the metal ions did not interfere with the extraction of DNA and that the co-extraction of protein can be mitigated by performing the extraction under moderately acidic conditions. Data from 31P NMR spectroscopy suggest that a combination of electrostatic and π–π interactions dominate IL–DNA complexation and that the extraction is concentration dependant. An experimental study: Thermal performance of molten salt cavity receivers Applied Thermal Engineering, 50, Issue 1, 10 January 2013, 334-341 Qiangqiang Zhang, Xin Li, Chun Chang, Zhifeng Wang, Hong Liu In solar power plants, a molten salt receiver always works in unsteady state conditions. Therefore, it is necessary to research the thermal performance of a receiver in an unsteady state condition. For this purpose, an indoor testing system with a molten salt cavity receiver was developed. Experimental research was conducted to determine the thermal performance of a 100 kWt molten salt receiver. The effect of the input power and flow rate on the thermal performance of the receiver was investigated. In addition, a simple unsteady model was established to research the characteristics of the variation of the internal energy of the receiver and the characteristics of the heat loss. The results indicated that the efficiency of the receiver was in direct proportion to the flow rate. However, the influence was small. In the initial stage of the transient process, the increments of the internal energy of the receiver and the fluid were large (approximately 20% in the energy which is not removed by the mass flow of the fluid). Over time, the thermal inertia of the receiver decreased with the transient ___________________________________________________________________________ page 190 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS process. As a result, any energy not taken away by the fluid was transformed into heat loss. Novel hybrid fluoro-carboxylated copolymers deposited by initiated chemical vapor deposition as protonic membranes Polymer, 54, Issue 1, 8 January 2013, 24-30 Anna Maria Coclite, Peter Lund, Rosa Di Mundo, Fabio Palumbo Copolymers of 1H, 1H, 2H, 2H,-perfluorodecyl acrylate and methacrylic acid are synthesized by initiated chemical vapor deposition (iCVD) to serve as proton exchange membranes for potential application in miniaturized fuel cells. The copolymerization of hydrophobic and hydrophilic monomers is difficult by conventional liquid-phase technique. We demonstrate that the use of iCVD is very promising for the synthesis of these membranes. Changing the monomer feed ratio we have a systematical control over the copolymer composition. The calculation of the copolymer ratios shows a moderate alternate composition of the copolymer which is advantageous to obtain highly conductive (acid functionalities) and stable (hydrophobic functionalities) membrane in the operating conditions of the fuel cells. The copolymers show a high degree of chain mobility when passing from dry to hydrated state as demonstrated by XPS analysis and by the high water contact angle hysteresis measured (>30°). An ionic conductivity of 70 mS/cm is obtained in conditions of highest percentage of hydrophobic functionalities. This conductivity value is comparable with the ionic conductivity of commercial Nafion®. Ionic liquid oxidation synthesis of Ag@AgCl core–shell structure for photocatalytic application under visible-light irradiation Colloids and Surfaces A: Physicochemical and Engineering Aspects, 416, 5 January 2013, 80-85 Yuanguo Xu, Hui Xu, Huaming Li, Jia Yan, Jiexiang Xia, Sheng Yin, Qi Zhang Ag@AgCl core–shell nanocomposite was synthesized by using [Bmim]FeCl4 IL etching Ag nanowires into Ag@AgCl in solution at room temperature. The obtained samples exhibited highly visible-light photocatalytic ability for the degradation of methyl orange and 4-chlorophenol in water solution. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ag and AgCl crystals. Scanning electron microscopy (SEM) images and X-ray energy-dispersive spectroscopy (EDS) of the samples revealed that AgCl nanoparticles (NPs) formed on the surface of Ag nanowires. UV–vis spectroscopy showed that Ag@AgCl core–shell structure enhanced its absorption in the visible-light region. The results showed that the absorption ability of Ag@AgCl was related to the change of Ag@AgCl. The absorption ability of the samples increased with the increasing etching time, and the enhancing photocatalytic ability was due to the increasing plasmonic absorbance ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 191 PUBLICATIONS of the photocatalysts. The effect of the etching time on the photocatalyst activity was studied, and the reaction mechanism was proposed. Conductivity and electrochemical performance of cathode xLi2MnO3·(1 − x)LiMn1/3Ni1/3Co1/3O2 (x = 0.1, 0.2, 0.3, 0.4) at different temperatures Journal of Alloys and Compounds, 546, 5 January 2013, 239-245 Chuang Yu, Heng Wang, Xiangfeng Guan, Jing Zheng, Liping Li In this work, the conductivity and electrochemical performance of compounds xLi2MnO3·(1 − x)LiMn1/3Ni1/3Co1/3O2 (x = 0.1, 0.2, 0.3, 0.4) at temperature −10, 25, and 45 °C were investigated. Both conductivity and electrochemical performance are dependent on the content of Li2MnO3 (x). The compound with x = 0.3 has a highest AC conductivity of 4.36 × 10−6 S cm−1 at room temperature. The conductivity is 8.64 × 10−7 S cm−1 at −10 °C, one order smaller than 9.98 × 10−6 S cm−1 at 45 °C. Furthermore, at a current density of 50 m Ag−1, the compound with composition at x = 0.3 showed an initial discharge capacity of 223.67 mA hg−1 at room temperature, which increased to 238.08 mA hg−1 at 45 °C and decreased to 114.5 mA hg−1 when testing temperature was decreased to −10 °C. Increasing the conductivity is an effective way to get better electrochemical performances of this kind of compound at different temperatures. Determination of ultraviolet filters in environmental water samples by temperature-controlled ionic liquid dispersive liquid-phase microextraction Journal of Chromatography A, 1271, Issue 1, 4 January 2013, 56-61 Yufeng Zhang, Hian Kee Lee In the present study, a rapid, highly efficient and environmentally friendly sample preparation method named temperature-controlled ionic liquid dispersive liquid-phase microextraction (TC-IL-DLPME), followed by high performance liquid chromatography (HPLC) was developed for the extraction, preconcentration and determination of four benzophenone-type ultraviolet (UV) filters (viz. benzophenone (BP), 2-hydroxy-4-methoxybenzophenone (BP-3), ethylhexyl salicylate (EHS) and homosalate (HMS)) from water samples. An ultra-hydrophobic ionic liquid (IL) 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]), was used as the extraction solvent in TC-IL-DLPME. Temperature served two functions here, the promotion of the dispersal of the IL to the aqueous sample solution to form infinitesimal IL drops and increase the interface between them and the target analytes (at high temperature), and the facilitation of mass transfer between the phases, and achievement of phase separation (at low temperature). Due to the ultra-hydrophobic feature and high density of the extraction solvent, complete phase separation could be effected by centrifugation. Moreover, no disperser solvent was required. Another prominent feature of the procedure was the ___________________________________________________________________________ page 192 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS combination of extraction and centrifugation in a single step, which not only greatly reduced the total analysis time for TC-IL-DLPME but also simplified the sample preparation procedure. Various parameters that affected the extraction efficiency (such as type and of extraction solvent, temperature, salt addition, extraction time and pH) were evaluated. Under optimal conditions, the proposed method provided good enrichment factors in the range of 240–350, and relative standard deviations (n = 5) below 6.3%. The limits of detection were in the range of 0.2–5.0 ng/mL, depending on the analytes. The linearities were between 1 and 500 ng/mL for BP, 5 and 1000 ng/mL for BP-3, 10 and 1000 ng/mL for HMS and 5 and 1000 ng/mL for EHS. Finally, the proposed method was successfully applied to the determination of UV filters in swimming pool and tap water samples and acceptable relative recoveries over the range of 88.0–116.0% were obtained. Gas chromatographic retention of alkyl phosphates on ionic liquid stationary phases Journal of Chromatography A, 1271, Issue 1, 4 January 2013, 170-175 Brandon M. Weber, James J. Harynuk Retention behaviors of alkyl phosophates were studied on a series of ionic liquid gas chromatography columns. The selectivity of the IL columns for alkyl phosphates were compared with a 5% phenyl column as a route to evaluating the potential use of IL columns in the analysis of alkyl phosphates in petroleum samples in both one- and multi-dimensional GC. Most interestingly, we demonstrate for the first time the dependence of elution order on separation temperature for members of a homologous series of compounds. At low temperatures it was found that trihexyl phosphate eluted before trioctyl phosphate, while at higher temperatures this pattern was reversed. Ionic liquids-based microwave-assisted extraction of active components from pigeon pea leaves for quantitative analysis Separation and Purification Technology, 102, 4 January 2013, 75-81 Zuofu Wei, Yuangang Zu, Yujie Fu, Wei Wang, Meng Luo, Chunjian Zhao, Youzhi Pan The present study aims to extract active components from pigeon pea leaves by ionic liquid-based microwave-assisted extraction (ILMAE) for quantitative analysis. Compared with ionic liquid-based heating extraction (ILHE) and ultrasonic-assisted extraction (ILUAE), ILMAE exhibited higher extraction efficiency. A series of 1-alkyl-3-methylimidazolium ILs with different anions and alkyl chain lengths of cations were investigated, and 1-butyl-3methylimidazolium bromide ([C4MIM]Br) solution was selected as extractants. Subsequently, ILMAE parameters were optimized, and the optimized conditions were [C4MIM]Br concentration 0.75 M, extraction temperature 60 °C, solvent to solid ratio 12:1 mL/g, and irradiation time 7 min. Under the optimal ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 193 PUBLICATIONS conditions, the extraction efficiency increased by 11.0–38.9% compared with ILHR and ILUAE, and the recovery achieved more than 95.3%. Furthermore, a rapid analysis method, HPLC-DAD with an UPLC column, was established and validated. This method exhibited satisfactory linearity (r2 > 0.999), precision (RSD < 4.6%) and recovery (97.14–103.38%), and was successfully applied for the quantification of nine components in pigeon pea leaves within 25 min. The results obtained provide a fast and safe method for determination of active components in pigeon pea leaves. A novel amperometric biosensor for superoxide anion based on superoxide dismutase immobilized on gold nanoparticle-chitosan-ionic liquid biocomposite film Analytica Chimica Acta, 758, 3 January 2013, 66-71 Lu Wang, Wei Wen, Huayu Xiong, Xiuhua Zhang, Haoshuang Gu, Shengfu Wang A novel superoxide anion (O2•−) biosensor is proposed based on the immobilization of copper-zinc superoxide dismutase (SOD) in a gold nanoparticle-chitosan-ionic liquid (GNPs-CS-IL) biocomposite film. The SODbased biosensor was constructed by one-step ultrasonic electrodeposition of GNP-CS-IL composite onto glassy carbon electrode (GCE), followed by immobilization of SOD on the modified electrode. Surface morphologies of a set of representative films were characterized by scanning electron microscopy. The electrochemical performance of the biosensor was evaluated by cyclic voltammetry and chronoamperometry. A pair of quasi-reversible redox peaks of SOD with a formal potential of 0.257 V was observed at SOD/GNPs-CSIL/GCE in phosphate buffer solution (PBS, 0.1 M, pH 7.0). The effects of varying test conditions on the electrochemical behavior of the biosensor were investigated. Furthermore, several electrochemical parameters were calculated in detail. Based on the biomolecule recognition of the specific reactivity of SOD toward O2•−, the developed biosensor exhibited a fast amperometric response (<5 s), wide linear range (5.6–2.7 × 103 nM), low detection limit (1.7 nM), and excellent selectivity for the real-time measurement of O2•−. The proposed method is promising for estimating quantitatively the dynamic changes of O2•− in biological systems. Gas phase electronic absorption spectroscopy of room temperature ionic liquids: N-Ethyl-3-methylpyridinium or 1-butyl-3-methylimidazolium cation with bis(trifluoromethylsulfonyl)amido anion Chemical Physics Letters, 555, 3 January 2013, 110-114 Takahiro Ogura, Nobuyuki Akai, Akio Kawai, Kazuhiko Shibuya Ultraviolet absorption spectra of ionic liquids, N-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)amido (EmpyTf2N) and 1-butyl-3methylimidazolium Tf2N (BmimTf2N) were measured in the gas phase by a ___________________________________________________________________________ page 194 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS cavity ring-down and a conventional single-path absorption methods. The vapor pressures at 400–430 K were derived from the measured absorbance, and the vaporization enthalpies were determined as 162 ± 35 and 137 ± 11 kJ mol−1 for EmpyTf2N and BmimTf2N, respectively. There are no remarkable spectral shifts between the absorption spectra in gas phase and neat liquid conditions, which are discussed based on the solvation model of the Onsager reaction field. Microwave synthesis of cellulose/CuO nanocomposites in ionic liquid and its thermal transformation to CuO Carbohydrate Polymers, 91, Issue 1, 2 January 2013, 162-168 Ming-Guo Ma, Shao-Jun Qing, Shu-Ming Li, Jie-Fang Zhu, Lian-Hua Fu, RunCang Sun The purpose of this study is to develop a green strategy to synthesize the cellulose-based nanocomposites and open a new avenue to the high value-added applications of biomass. Herein, we reported a microwave-assisted ionic liquid route to the preparation of cellulose/CuO nanocomposites, which combined three major green chemistry principles: using environmentally friendly method, greener solvents, and sustainable resources. The influences of the reaction parameters including the heating time and the ratio of cellulose solution to ionic liquid on the products were discussed by X-ray powder diffraction, Fourier transform infrared spectrometry, and scanning electron microscopy. The crystallinity of CuO increased and the CuO shape changed from nanosheets to bundles and to particles with increasing heating time. The ratio of cellulose solution to ionic liquid also affected the shapes of CuO in nanocomposites. Moreover, CuO crystals were obtained by thermal treatment of the cellulose/CuO nanocomposites at 800 °C for 3 h in air. A novel process for the synthesis of 3,5-diaryl-1,2,4-thiadiazoles from aryl nitriles Tetrahedron Letters, 54, Issue 1, 2 January 2013, 9-11 Jalil Noei, Ahmad Reza Khosropour A novel and efficient process for the synthesis of 3,5-diaryl-1,2,4-thiadiazoles from aryl nitriles in 1-butyl-3-methylimidazolium bromide promoted by (NH4)2S and TCT–DMSO is described. Synthesis and thermophysical properties of ionic liquids: cyclopropyl moieties versus olefins as Tm-reducing elements in lipid-inspired ionic liquids Tetrahedron Letters, 54, Issue 1, 2 January 2013, 12-14 Man-Lung Kwan, Arsalan Mirjafari, John R. McCabe, Richard A. O’Brien, David F. Essi IV, Leah Baum, Kevin N. West, James H. Davis Jr. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 195 PUBLICATIONS Cyclopropyl moieties embedded in the long aliphatic side chains of imidazolium-type ionic liquids are shown to be highly effective in lowering the Tm of such materials relative to counterparts bearing linear, saturated side chains. While not as efficient as olefins in bringing about this effect, ILs incorporating side-chain cyclopropanated modules are likely to be more resistant to aerobic degradation than those employing the former. Chapter Four - NMR Studies of Molten Salt and Room Temperature Ionic Liquids Annual Reports on NMR Spectroscopy, 78, 2013, 149-207 Anne-Laure Rollet, Catherine Bessada This chapter presents the nuclear magnetic resonance (NMR) developments and studies on the high temperature inorganic molten salts and on room temperature ionic liquids. It is focused on the liquid structure investigated, thanks to the chemical shifts analysis and to magnetization transfer experiments. It deals also with the dynamics at the local scale investigated using relaxometry and at the long range using pulsed field gradient NMR. Graphene sheets synthesized by ionic-liquid-assisted electrolysis for application in water purification Applied Surface Science, 264, 1 January 2013, 329-334 Chia-Feng Chang, Quang Duc Truong, Jiann-Ruey Chen A facile and green synthesis of graphene sheets by ionic-liquid-assisted electrolysis was investigated in this work. The synthesized graphene sheets have been studied using transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray powder diffraction (XRD), Raman spectroscopy (Raman) and Fourier transform infrared (FTIR) analysis. The obtained graphene was used for the adsorption of Fe2+ whose presence in the drinking water in wide areas of South Asia has been widely known. The result shows that the graphene could absorb Fe2+ with a capacity of 299.3 mg/g which is 6 times higher than that of graphite oxide. The adsorption properties of metal ions on graphene and the effects of various factors on the adsorption capacity were also investigated in detail. The research results suggest a novel material for developing highly efficient water purification materials for the developing economies. Polymeric ionic liquid (PIL)-supported recyclable catalysts for biomass conversion into HMF Biomass and Bioenergy, 48, January 2013, 181-190 Dajiang (D.J.) Liu, Eugene Y.-X. Chen This contribution reports the first study of recyclable PIL-supported metal (Cr, Al) catalysts for effective biomass (glucose and cellulose) conversion into 5___________________________________________________________________________ page 196 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS hydroxymethylfurfural (HMF), a key biorefining building block and biomass platform chemical. Of the five different PILs investigated, poly(3-butyl-1vinylimidazolium chloride), P[BVIM]Cl, has been found to be most effective; when combined with CrCl2 in situ or used as the preformed PIL-metalate P[BVIM]+[CrCl3]− in DMF, this PIL-supported catalyst converts glucose to HMF in 65.8% yield at 120 °C for 3 h. This yield is higher than those achieved by the catalysts based on the PIL monomer, [BVIM]Cl–CrCl2, as well as by the most commonly used molecular IL based catalyst, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl)–CrCl2, under otherwise identical conditions. The P[BVIM]Cl–CrCl2 catalyst system also works well for the cellulose-to-HMF conversion via a two-step process. The analogous PIL–Al catalyst, P[BVIM]Cl– Et2AlCl, is less effective than the PIL–CrCl2 system, but recyclability tests indicate the PIL–Al system is more recyclable thus achieving a nearly constant HMF yield upon 6 cycles. Influence of acidic and alkaline aqueous regeneration on enzymatic digestibility of the cellulose fraction recovered from [amim]Cl-treated rice husk Bioresource Technology, 128, January 2013, 330-336 Anika Salanti, Luca Zoia, Paola Frigerio, Marco Orlandi The recalcitrance of lignocelluloses toward enzymatic hydrolysis necessitates pretreatments. Ionic liquid pretreatment with 1-allyl-3-methylimidazolium chloride ([amin]Cl) was applied to risk husk and cellulose-containing fractions were recovered from the ionic liquid solutions by acidic, alkaline, and alkaline– acidic regeneration respectively. Enzymatic hydrolysis of the recovered materials was carried out and results demonstrated that: (i) acidic regeneration was not substantial to ensure enhanced enzymatic digestibility; (ii) alkaline regeneration increased the enzymatic hydrolysis; (iii) alkaline–acidic regeneration led to an almost complete hydrolysis of the carbohydrate fraction. The obtained results were rationalized by means of chromatographic analyses of soluble fractions collected after the different regeneration processes: the removal of hemicellulose, which increased going from the acidic to the alkaline–acidic regeneration, seemed to play a crucial role in enhancing the rice husk saccharification. Enhancement of the selective enzymatic biotransformation of rutin to isoquercitrin using an ionic liquid as a co-solvent Bioresource Technology, 128, January 2013, 156-163 Jun Wang, Guo-Xia Sun, Liang Yu, Fu-An Wu, Xi-Jie Guo An ionic liquid (IL)-containing buffer system was first applied in the conversion of rutin to isoquercitrin. High substrate solubility was achieved to enhance the selectivity and efficiency of hesperidinase-catalyzed reaction. Ten ILs were selected as co-solvents to assist catalytic reactions in this biotransformation ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 197 PUBLICATIONS process. The transformed products of rutin were identified by LC–MS. The [Bmim][BF4]-glycine-sodium hydroxide buffer (pH 9) (10:90, v/v) was found to be the best medium for the biotransformation of isoquercitrin from rutin with higher selectivity and efficiency. The reaction time was reduced by 0.33-fold while the conversion of rutin and the yield of isoquercitrin were increased by 1.67-fold and 2.33-fold. The results suggest that IL co-solvents have great potential to enhance the selectively enzymatic hydrolysis of rutin for isoquercitrin production. Effect of ionic liquid weight ratio on pretreatment of bamboo powder prior to enzymatic saccharification Bioresource Technology, 128, January 2013, 188-192 Kazuaki Ninomiya, Hiroshi Soda, Chiaki Ogino, Kenji Takahashi, Nobuaki Shimizu The pretreatment efficiency of weight ratios ranging from 0 to 10 of the ionic liquid, cholinum IL, to bamboo powder was investigated. An IL/biomass ratio of 3 g/g was critical to obtain a cellulose saccharification ratio of 80%. At this ratio, the treated bamboo powder remained as a solid. The solid-state pretreatment required a minimum amount of cholinium IL, which could reduce the cost of IL-assisted pretreatment and reduce the amount of wastewater generated in the process. Oil removal from water with yellow horn shell residues treated by ionic liquid Bioresource Technology, 128, January 2013, 673-678 Ji Li, Meng Luo, Chun-Jian Zhao, Chun-Ying Li, Wei Wang, Yuan-Gang Zu, Yu-Jie Fu In the present study, yellow horn shell residues treated by ionic liquid (IL) were prepared for oil removal from water. Scanning electron microscope (SEM) analysis was applied to represent the effects of IL-treatment on this new cellulosic biosorbent. Furthermore, the comprehensive sorption capacities of the shell residues for five types of oils in pure oil and oily water medium were evaluated. The maximum sorption capacities of IL-treated shell residues (0.39– 0.61 g/g) were about 1.5-fold to those of untreated shell residues (0.32– 0.42 g/g), respectively. The effects of main environmental factors (temperature and pH) on oil removal were also studied. Kinetic models were successfully established for analyzing the oil sorption process. In addition, it was found that the IL-treated shell residues could be reused for several times. The results indicated that IL-treated yellow horn shell residues could be developed as an ideal biosorbent for oil removal from water. Improved refining properties of pulps pretreated with ionic liquids under mild conditions ___________________________________________________________________________ page 198 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Bioresource Technology, 128, January 2013, 813-817 Zhiqiang Pang, Jiachuan Chen, Cuihua Dong, Guihua Yang, Yu Liu Imidazolium-based ionic liquids (ILs), including 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-allyl-3-methylimidazolium chloride (AmimCl), were used to improve the refining properties of pulps under mild conditions. Results showed that the macro appearance of pulps was virtually unchanged after pretreatment with ILs under mild conditions. In addition, chemical pulps pretreated with ILs are more suitable for pretreatment than chemimechanical pulps. Pretreatment with ILs facilitates the refining process by destroying hydrogen bonds, which exist extensively in fiber. At the same refining energy input, the Canada standard freeness (CSF) of refined pulp decreased with improved fiber quality. At identical CSF values, the energy consumed during refining significantly decreased because ILs pretreatment facilitated swelling and fibrillation. The viscosity of cellulose changed slightly after IL pretreatment. However, the crystallinity index and fines content decreased, and the micro appearance of the fiber surface changed. BmimCl has a stronger swelling influence on pulp than AmimCl under optimal conditions. Comparison of the impact of ionic liquid pretreatment on recalcitrance of agave bagasse and switchgrass Bioresource Technology, 127, January 2013, 18-24 Jose A. Perez-Pimienta, Monica G. Lopez-Ortega, Patanjali Varanasi, Vitalie Stavila, Gang Cheng, Seema Singh, Blake A. Simmons Lignocellulose represents a sustainable source of carbon for transformation into biofuels. Effective biomass to sugar conversion strategies are needed to lower processing cost without degradation of polysaccharides. Since ionic liquids (ILs) are excellent solvents for pretreatment/dissolution of biomass, IL pretreatment was carried out on agave bagasse (AGB-byproduct of tequila industry) and digestibility and sugar yield was compared with that obtained with switchgrass (SWG). The IL pretreatment was conducted using ([C2mim][OAc]) at 120 and 160 °C for 3 h and 15% biomass loading. While pretreatment using [C2mim][OAc] was very effective in improving the digestibility of both feedstocks, IL pretreatment at 160 °C resulted in higher delignification for AGB (45.5%) than for SWG (38.4%) when compared to 120 °C (AGB-16.6%, SWG8.2%), formation of a highly amorphous cellulose structure and a significant enhancement of enzyme kinetics. These results highlight the potential of AGB as a biofuel feedstock that can produce high sugar yields with IL pretreatment. Separation and characterization of cellulose fibers from cypress wood treated with ionic liquid prior to laccase treatment Bioresource Technology, 127, January 2013, 132-137 Muhammad Moniruzzaman, Tsutomu Ono ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 199 PUBLICATIONS Separation of cellulose fibers (CFs) from woody biomass with minimal structural alteration using a “green” and efficient method was achieved by treatment with the ionic liquid (IL), [emim][OAc] (1-ethyl-3-methylimidazolium acetate) at 80 °C for 1 h. The IL was recovered by rinsing with water–acetone mixture prior to treatment of the wood with Trametes sp. laccase in the presence of 1-hydroxybenzotriazole as a mediator. IL pretreatment did not significantly change the chemical composition of the wood, but did alter its structure and rendered its surface more accessible to the enzyme. Treated and untreated samples were characterized by SEM, FTIR, XRD, TGA, and chemical methods. The cellulose content of the produced fibers was approximately 73.1% and the lignin content was 9.8%, much lower than the lignin content of 29.3% of the untreated wood. The cellulose fibers exhibited higher cellulose crystallinity and better thermal stability compared to untreated wood materials. . Effects of debinding atmosphere on the microstructure and sintering densification of nickel ferrite Ceramics International, 39, Issue 1, January 2013, 865-869 Yuqiang Tao, Zhiyou Li, Kechao Zhou Microsized nickel ferrite (NiFe2O4) powders were synthesized by molten salt synthesis in KCl flux using Fe2O3 and NiO as raw materials. The binder burnout process of the compact containing 1.2 wt% poly vinyl alcohol was performed in air and N2 atmospheres, followed by sintering in N2 atmosphere. The effects of debinding atmosphere on the microstructure and sintering densification of NiFe2O4 were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS). Metallic Ni particles were found uniformly distributed on the surface of NiFe2O4 particles debound in N2 atmosphere. The densifications of the samples sintered at 1150 °C and 1300 °C were 90.7% and 97.2% respectively when the binder burnout process was performed in N2 atmosphere. They increased by 15% and 6.7% respectively compared with those debound in air. The temperature for the debound sample to reach a densification of 90% was 150 °C lower in N2 atmosphere than that in air. Also the average grain size of NiFe2O4 and Fe/Ni ratio in NiFe2O4 phase of the sintered samples debound in N2 atmosphere showed a significant increase, compared with those debound in air. Absorption of CO2 by amino acid-functionalized and traditional dicationic ionic liquids: Properties, Henry’s law constants and mechanisms Chemical Engineering Journal, 214, 1 January 2013, 355-363 Yi Zhang, Ping Yu, Yunbai Luo Six dicationic ionic liquids (DILs) were synthesized, including four amino acidfunctionalized DILs (AA-DILs) and two traditional DILs (T-DILs), and were found to be effective for CO2 capture as reversible absorbents. Their physical ___________________________________________________________________________ page 200 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS properties were measured, containing density, conductivity, thermal decomposition temperature, glass transition temperature and viscosity. Their CO2 absorption behaviors under different pressures and temperatures with various water contents were also investigated. The results showed that the CO2 absorption capacities of pure AA-DILs were enhanced heavily compared to other monocationic ionic liquids. Mixing AA-DIL and water could be combined in a more rapid and efficient manner for CO2 gas capture, superior to the use of pure DIL only, due to their visible decrease in viscosity. The effect of temperature on CO2 absorption by aqueous AA-DIL mixtures at ambient pressure was extremely obvious: when temperature rose from 30 to 50 °C, the capacity of the 60 wt% [Bis(mim)C4][Pro]2 solution decreased from 1.52 to 0.78 mol/mol; as the pressure rose up to 10.0 bar, the total maximal capacity also dropped by more than a half. On the other hand, the two traditional DILs also exhibited an excellent physical absorption compared to varieties of monocationic ionic liquids. One-step synthesis of composite semiconductor AgBr/Ag5P3O10 heterojunctions and their photocatalytic activity, kinetic analysis, photocatalytic mechanism under visible light radiation Chemical Engineering Journal, 214, 1 January 2013, 336-342 Limin Song, Shujuan Zhang, Xiaoqing Wu, Shuna Zhang, Haifeng Tian, Jiayi Ye A composite semiconductor AgBr/Ag5P3O10 heterojunction has been synthesized by a simple one-step ion-exchange process in Br ionic liquids. All the as-obtained AgBr/Ag5P3O10 heterojunctions were characterized by X-ray powder diffraction (XRD), scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), Brunauer–Emmett–Teller (BET), UV–vis absorption spectroscopy (UV–vis), photoluminescence (PL), and surface photovoltage (SPS) techniques. The as-prepared AgBr/Ag5P3O10 heterojunctions intensively absorb in the visible light region. The effects of different conditions on the photocatalytic properties were investigated systematically. The AgBr/Ag5P3O10 heterojunctions exhibited an enhanced photocatalytic activity than the individual Ag5P3O10 did in the degradation of methylene blue (MB) under visible-light irradiation. Much more •OH radicals were found in the AgBr/Ag5P3O10 system in comparison with those in Ag5P3O10 alone by analyzing the formed •OH radicals under visible light radiation. The SPS measurement shows that the SPS amplitude of AgBr/Ag5P3O10 heterojunctions was higher than that of Ag5P3O10, which indicates the higher charge separation efficiency of AgBr/Ag5P3O10 heterojunctions. Based on the above experimental results, the kinetic data and the photocatalytic mechanism of the AgBr/Ag5P3O10 heterojunctions were discussed in detail. Use of ion-exchange resins for the adsorption of the cationic part of ionic liquid, 1-ethyl-3-methylimidazolium ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 201 PUBLICATIONS Chemical Engineering Journal, 214, 1 January 2013, 78-82 Sun Beom Choi, Sung Wook Won, Yeoung-Sang Yun Ionic liquids (ILs) are low melting organic salts with wide potential applications due to their fascinating properties and have emerged as promising “green” replacements for volatile organic solvents. Despite their non-measurable vapor pressure, some ILs inevitably occur in effluent discharges since they do have significant solubility in water. Recently, the toxic effects of ILs toward aquatic communities have been intensively investigated, but little is known about their removal from industrial wastewater. This study proposes adsorption by ionexchange resins for the removal of the cationic part of the IL, 1-ethyl-3methylimidazolium acetate ([EMIM]OAc). Twelve ion-exchange resins with different functional groups like thiourea, iminodiacetic acid, aminophosphonic acid, carboxylic acid, and sulfonic acid were examined. The resins with sulfonic acid functional groups showed the highest sorption abilities ranging from 578.2 to 616.2 mg/g. Large bead size led to lower kinetics of [EMIM] adsorption. But the bead size and the degree of cross-linking of the resins insignificantly affected the sorption performance of [EMIM] cations. PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters Chemosphere, 90, Issue 4, January 2013, 1396-1403 Dezhao Liu, Anders Feilberg, Anders Michael Nielsen, Anders Peter S. Adamsen Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry’s law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using ProtonTransfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3– 45 °C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H2S, a higher enthalpy of air–liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that cosolute effects for sulfur compounds can be neglected in numerical biofilter ___________________________________________________________________________ page 202 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength. Estimation of Abraham solvation equation coefficients for hydrogen bond formation from Abraham solvation parameters for solute acidity and basicity Chemosphere, 90, Issue 2, January 2013, 344-348 Paul van Noort Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham solvation equations, this study derives equations, based on Abraham solvation parameters for hydrogen acidity and basicity of the solvents involved, to estimate the value of the coefficients for hydrogen bond formation. These equations were applied to calculate Abraham solvation parameters for hydrogen acidity and basicity for polyoxymethylene, polyacrylate, sodium dodecylsulfate, some ionic liquids, alkanoyl phosphatidyl cholines, and lipids for which fitted values for Abraham coefficients for hydrogen bond formation were available. Changes in zeta potential of imidazolium ionic liquids modified minerals – Implications for determining mechanism of adsorption Chemosphere, 90, Issue 2, January 2013, 706-712 Marta Markiewicz, Wojciech Mrozik, Kurosch Rezwan, Jorg Thöming, Jan Hupka, Christian Jungnickel As the amount of industrial processes involving ionic liquids (ILs) increase the question of their environmental fate awaits an answer. Should ILs become a source of pollution they will primarily be found in soils and water. Interaction of imidazolium IL with soils is a complex interplay of many parameters making predicting their fate and mobility a challenging task. In order to shed more light on the mechanism of adsorption in soils we examined the interactions of imidazolium ILs with the major component of soils, namely mineral fraction. Within this work adsorption on kaolinite and quartz was investigated in terms of adsorption isotherms, partition coefficients and changes of zeta potentials of clays modified by ILs aggregates. The zeta potential was found to be dependent on the alkyl chain length of the imidazolium homologues. It can therefore be concluded that although adsorption seems to rely on electrostatic attraction, at least in the initial stage, the hydrophobicity of molecules is just as significant. A new composite polymer electrolyte based poly(ethyleneoxide)/polysiloxane/BMImTFSI/organomontmorillonite Chinese Chemical Letters, 24, Issue 1, January 2013, 70-72 Yue-Jiao Li, Feng Wu, Hu-Ren Chao, Shi Chen on ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 203 PUBLICATIONS Composite polymer electrolytes based on poly(ethylene oxide)–polysiloxane/1butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide/organomontmorillonite (PEO– PDMS/IL/OMMT) were prepared and characterized. Addition of both an ionic liquid and OMMT to the polymer base of PEO–PDMS resulted in an increase in ionic conductivity. At room temperature, the ionic conductivity of sample PPB100–OMMT4 was 2.19 × 10−3 S/cm. The composite polymer electrolyte also exhibited high thermal and electrochemical stability and may potentially be applied in lithium batteries. Application of Fe3O4 mesoporous sphere modified carbon ionic liquid electrode as electrochemical hemoglobin biosensor Colloids and Surfaces B: Biointerfaces, 101, 1 January 2013, 177-182 Wei Sun, Zhaolan Sun, Liqi Zhang, Xiaowei Qi, Guangjiu Li, Jie Wu, Mei Wang A new electrochemical hemoglobin (Hb) biosensor was constructed based on a Fe3O4 mesoporous spheres modified carbon ionic liquid electrode (CILE), which showed excellent electrocatalytic ability towards the reduction of trichloroacetic acid. CILE was prepared by using N-hexylpyridinium hexafluorophosphate (HPPF6) as the modifier and the binder in the carbon paste. Ultraviolet-visible and Fourier transform infrared spectroscopic results indicated that Hb molecules retained the native structure in the chitosan and Fe3O4 mesoporous spheres composite film. Electrochemical results indicated that a pair of well-defined redox peaks appeared in 0.1 mol/L phosphate buffer solution (PBS) with the formed potential (E0′) as −0.287 V (vs. SCE), indicating that the direct electron transfer of Hb in the composite film was realized. Electrochemical behaviors of Hb were carefully investigated with the electrochemical parameters such as electron transfer coefficient (α), electron transfer number (n), and heterogeneous electron transfer rate constant (ks) calculated. Due to the specific characteristics of Fe3O4 mesoporous spheres present on the electrode surface, the electron transfer rate of Hb was greatly promoted. The Hb modified electrode exhibited excellent electrocatalytic properties with wider linear range and lower detection limit. Physicochemical characterization of tensio-active produced by Geobacillus stearothermophilus isolated from petroleum-contaminated soil Colloids and Surfaces B: Biointerfaces, 101, 1 January 2013, 315-318 Alícia M.A.T. Jara, Rosileide F.S. Andrade, Galba M. Campos-Takaki Biosurfactants are surface-active agents of microbial origin, and have a property of lowering the interfacial tension between two liquids. They act on the interface and are amphiphathic molecules; in with both hydrophilic and hydrophobic portions are present in the same molecule. However, the economics of ___________________________________________________________________________ page 204 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS producing biosurfactant has limited its commercial applications, and the costs can be reduced using cheap substrates or industrial waste. The present study showed the biosurfactant production using corn steep liquor and palm oil as carbon and nitrogen sources for reduction the costs of production. The biosurfactant production by Geobacillus stearothermophilus UCP 986 was carried out using optimized culture medium constituted by palm oil (7.5%) and corn steep liquor (4.5%) using Bioflo fermentor, at temperature of 45 °C, during 32 h and agitation of 300 rpm. The biosurfactant showed a reduction of the water surface tension of 72–31 mN/m and interfacial tension of 0.3 mN/m. The biosurfactant was obtained from the net metabolic liquid by acetone precipitation corresponding to the yield of 2.3 g/L. The isolate biosurfactant showed a CMC of 2.5% and non-ionic profile. The best emulsification index (E24) obtained was 87% using motor oil burned. The biosurfactant solution (2.5%) used in oil spreading test increases the viscosity of engine burning oil of 149.2% and 138.2% to vegetable fat post-frying, respectively. The gas chromatography–mass spectrometer indicated at 29.52 min a molecular weight of 207 Da and eight peaks by FT-IR identified the chemical structure of the biosurfactant produced by G. stearothermophilus. Interactions between ionic liquid surfactant [C12mim]Br and DNA in dilute brine Colloids and Surfaces B: Biointerfaces, 101, 1 January 2013, 398-404 Yunfei He, Yazhuo Shang, Zhenhai Liu, Shuang Shao, Honglai Liu, Ying Hu Interactions between ionic liquid surfactant [C12mim]Br and DNA in dilute brine were investigated in terms of various experimental methods and molecular dynamics (MD) simulation. It was shown that the aggregation of [C12mim]Br on DNA chains is motivated not only by electrostatic attractions between DNA phosphate groups and [C12mim]Br headgroups but also by hydrophobic interactions among [C12mim]Br alkyl chains. Isothermal titration calorimetry analysis indicated that the [C12mim]Br aggregation in the presence and absence of DNA are both thermodynamically favored driven by enthalpy and entropy. DNA undergoes size transition and conformational change induced by [C12mim]Br, and the charges of DNA are neutralized by the added [C12mim]Br. Various microstructures were observed such as DNA with loose coil conformation in nature state, necklace-like structures, and compact spherical aggregates. MD simulation showed that the polyelectrolyte collapses upon the addition of oppositely charged surfactants and the aggregation of surfactants around the polyelectrolyte was reaffirmed. The simulation predicted the gradual neutralization of the negatively charged polyelectrolyte by the surfactant, consistent with the experimental results. Fabrication of carbon fiber reinforced aluminum matrix composites via a titanium-ion containing flux ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 205 PUBLICATIONS Composites Part A: Applied Science and Manufacturing, 44, January 2013, 4750 P. Baumli, J. Sychev, I. Budai, J.T. Szabo, G. Kaptay Here we show that carbon fiber (CF) reinforced aluminum (Al) matrix composite with homogenously dispersed (57 ± 11 vol.%) carbon fibers can be fabricated without any external pressure, although usually some external pressure is needed to fabricate such composites due to their non-wetting character. CFs were transferred into liquid Al using a special flux (molten salt), containing K2TiF6 dissolved in NaCl–KCl. This flux ensures the removal of oxides from the interfaces and the formation of a wettable TiC layer at the interfaces. The oxide-free and in situ TiC-coated CF showed perfect wettability by the de-oxidized liquid Al under the same flux, and thus the composite was formed in a spontaneous way, i.e. without applying any external pressure or mixing. Thermodynamic description of the M2O–SiO2 (M = K, Na) systems Computational Materials Science, 66, January 2013, 20-27 Ligang Zhang, Clemens Schmetterer, Patrick J. Masset The phase diagrams of the M2O–SiO2 (M = K, Na) binary systems were assessed using the Calculation of Phase Diagram (CALPHAD) technique. The thermochemical and phase equilibrium information taken from the literature for these two binary systems have been evaluated, and a series of thermodynamic parameters was obtained to describe each phase in these systems. The liquid phase was described by the ionic two-sublattice model with the formula (M+1)P(O-2,SiO4-4,SiO20,Va-)Q (M = K, Na). The heat capacities of solid phases were taken into consideration in this optimization process, a brief review of which is given in this work. The calculated phase equilibria were found to be in agreement with available experimental data. Study of alkyl chain length dependent characteristics of imidazolium based ionic liquids [CnMIM]+[TFSA]− by Brillouin and dielectric loss spectroscopy Current Applied Physics, 13, Issue 1, January 2013, 271-279 Hyun-Joung Kwon, Jeong-Ah Seo, Takashi Iwahashi, Yukio Ouchi, Doseok Kim, Hyung Kook Kim, Yoon-Hwae Hwang This study examined the acoustic phonon mode of ionic liquids consisting of 1alkyl-3-methyl-imidazolium family (CnMIM) cations with n values ranging from 2 to 10 and bis(trifluoromethylsulfonyl)amide (TFSA) anion in the temperature range from 300 K to 100 K. [CnMIM]+[TFSA]− showed depolarized (VH) components of Brillouin peaks at temperatures below the glass transition temperature when n is larger than 4. On the other hand, in the case of ionic liquids with different anions, such as [C4MIM]+[BF4]−, [C4MIM]+[PF6]− and ___________________________________________________________________________ page 206 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS [C8MIM]+[BF4]−, the VH component of Brillouin peaks was not observed in the temperature range investigated. The dielectric loss spectra showed that the temperature dependence of alkyl chain domain relaxation of all ionic liquids followed the Arrhenius law and showed an increase in activation energy at the temperature where the VH component of Brillouin peak appeared. These results suggest that the observed depolarized component of Brillouin peak might originate from uniquely induced polarization in the 2nd domain composed of head groups of cations and anions. Comparison among the performance of LiBOB, LiDFOB and LiFAP impregnated polyvinylidenefluoride-hexafluoropropylene nanocomposite membranes by phase inversion for lithium batteries Current Applied Physics, 13, Issue 1, January 2013, 293-297 V. Aravindan, P. Vickraman, A. Sivashanmugam, R. Thirunakaran, S. Gopukumar This paper describes the physico-chemical and electrochemical properties of polyvinylidenefluoride-hexafluoropropylene (PVdF-HFP) membranes (GPM) prepared by phase inversion technique. Nanocomposite polymer membranes (NCPM) are also prepared by the same technique using AlO(OH)n nanoparticles. The prepared GPM and NCPM are gelled with liquid electrolyte containing three different salts namely, lithium bis(oxalate)borate, lithium fluoroalkylphosphate and lithium difluoro(oxalato)borate. Prepared membranes were subjected to various physico-chemical characterizations likely, mechanical stability, ionic conductivity, morphological studies, surface area and thermal analysis. Electrochemical chemical properties of membranes are evaluated in half-cell configurations (Li/NCPM or GPM/LiFePO4) at room temperature conditions. Galvanostatic cycling profiles clearly indicates the improved performance of chelato borate based anions i.e. BOB and DFOB when compared to fluoroalkyl group (FAP). Chapter 13.2 - Kaolinite–Polymer Nanocomposites Developments in Clay Science, 5, 2013, 707-719 C. Detellier, S. Letaief The rapid development of clay–polymer nanocomposites (CPN) in the last two decades was mainly focused on the use of delaminated smectites as inorganic nanofillers. Because the nature and the structure of the aluminosilicate should have an effect on the CPN properties, there is a need to develop the delamination chemistry of layered minerals other than those of the smectite group. The chemistry of modification of kaolin group minerals, in particular, kaolinite intercalation, is much more challenging than in the case of the smectites, but the remarkable and quite unique structural characteristics of this clay mineral could counterbalance the difficulties of the intercalation processes. The knowledge regarding the synthesis of new hybrid materials with controlled ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 207 PUBLICATIONS morphology derived from kaolinite is increasing. This chapter reviews the progress of the intercalation chemistry of kaolino and preparation and characterization of delaminated and exfoliated CPN. It shows the progress achieved in the interlayer grafting of organic units on the aluminol groups of the interlayer surfaces of kaolinite and dickite, or to the siloxane groups in the case of halloysite. Also reported are the preparation of intercalated CPN and the intercalation of ionic liquids, leading to the formation of nanohybrid materials with relatively large, functional organic units organized in the confined twodimensional interlayer space of the clay mineral. β-Carotene: A green, inexpensive, and convenient solvatochromic probe for the determination of solvent polarizability Dyes and Pigments, 96, Issue 1, January 2013, 16-24 Carina Loffredo, Paulo Augusto R. Pires, Muhammad Imran, Omar A. El Seoud Solvent polarizability has been previously determined by using the solvatochromic probe 3,20-di-tert-butyl-2,2,21,21-tetramethyl3,5,7,9,11,13,15,17,19-docosanonaene whose synthesis involves 15 steps. We show here that the natural dye β-carotene, 1,1′-(3,7,12,16-tetramethyl1,3,5,7,9,11,13,15,17-octadecanonaene-1,18-diyl)bis[2,6,6trimethylcyclohexene], can be conveniently employed for the accurate determination of the same solvent property. This conclusion is based on both theoretical calculations and experimental data. The former includes free energies of solvation, and the wavenumber of the longest wavelength (i.e., the solvatochromic) transition. Both quantities for β-carotene correlate linearly with the corresponding values of the docosanonaene, with slopes and correlation coefficients of practically unity. The plot of experimentally calculated solvent polarizability of β-carotene versus that of the docosanonaene was found to be linear for 68 solvents. Previously unknown solvent polarizability values are reported for eight ROCH2CH2OH (R = C1 to C10) and four 1-allyl-3-Rimidazolium chloride ionic liquids (R = C6 to C10). The dependence of solvent polarizability on the number of carbon atoms in the hydrocarbon chains of several classes of solvents is calculated, it shows the importance of van der Waals interactions in ionic liquids. Elicitation of the most important structural properties of ionic liquids affecting ecotoxicity in limnic green algae; a QSAR approach Ecotoxicology and Environmental Safety, 87, 1 January 2013, 42-48 Parisa Izadiyan, M.H Fatemi, Mahsa Izadiyan Many ionic liquids are soluble in water and their impact on the aquatic environment has to be evaluated. However, due to the large number of ionic liquids and lack of experimental data, it is necessary to develop estimation procedures in order to reduce the materials and time consumption. In this study using multilayer perceptron neural network (MLP), ant colony optimization ___________________________________________________________________________ page 208 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS (ACO) and multiple linear regression (MLR) strategies, good predictive quantitative structure–activity relationships (QSAR) models were introduced and structural parameters affecting ecotoxicity of ionic liquids in limnic green algae (Scenedesmus vacuolatus) were revealed. Moreover, principal component analysis (PCA) and cluster analysis (CA) approaches were also applied to visualize any possible patterns or relationships among ionic liquids data. It was revealed that selected descriptors of the MLR model are also capable of clustering ionic liquids according to their four level of toxicity. Synthesis and anti-microbial potencies of 1-(2-hydroxyethyl)-3alkylimidazolium chloride ionic liquids: Microbial viabilities at different ionic liquids concentrations Ecotoxicology and Environmental Safety, 87, 1 January 2013, 65-69 M. Ismail Hossain, Mohanad El-Harbawi, Noorjahan Banu Mohamed Alitheen, Yousr Abdulhadi Noaman, Jean-Marc Lévêque, Chun-Yang Yin Three 1-(2-hydroxyethyl)-3-alkylimidazolium chloride room temperature ionic liquids (ILs) [2OHimCn][Cl]; (n=0, 1, 4) have been synthesized from the appropriate imidazole precursors and characterized by IR and NMR spectroscopies and elemental analysis. Their anti-microbial activities were investigated using the well-diffusion method. The viabilities of Escherichia coli, Aeromonas hydrophila, Listeria monocytogenes and Salmonella enterica as a function of IL concentrations were studied. The minimal inhibitory concentrations (MICs) and EC50 values for the present ILs were within the concentration range from 60 to 125 mM and 23 to 73 mM. The anti-microbial potencies of the present ILs were compared to a standard antibiotic, gentamicin. The finding affords additional perspective on the level of ILs toxicity to aquatic lifeforms and yet, this characteristic can be readily harnessed to detect microbial growth and activity. A PRS model for accurate prediction of the optimal solid oxide cathode structure for the preparation of metals in molten chlorides Electrochemistry Communications, 26, January 2013, 33-36 Hualin Chen, Yi Zeng, Wei Li, Junjun Peng, Xianbo Jin, George Z. Chen A theoretical model correlating the precursor porosity, P (in percentage), the metal-to-oxide molar ratio, R, and the cathode shrinkage S (in fraction, experimentally determined) (the PRS model) with the deoxidation speed of the solid metal oxide cathode in molten chlorides has been developed, allowing accurate prediction of the optimal cathode porosity by a simple equation, . Tests of this equation in practices suggest Popt to be an intrinsic parameter to the oxide. For example, the predicted values of Popt for the electrolysis of TiO2 and Ta2O5 cathodes are about 67% and 25% respectively, and a cathode porosity far away from Popt would suppress the deoxidation ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 209 PUBLICATIONS seriously. The established model has been well verified by the electrolysis of the oxides of Si, Ti and Ta. AgSbS2 semiconductor-sensitized solar cells Electrochemistry Communications, 26, January 2013, 48-51 Yi-Rong Ho, Ming-Way Lee We present a ternary semiconductor nanoparticle sensitizer – AgSbS2 – for solar cells. AgSbS2 nanoparticles were grown using a two-stage successive ionic layer adsorption and reaction process. First, Ag2S nanoparticles were grown on the surface of a nanoporous TiO2 electrode. Secondly, a Sb–S film was coated on top of the Ag2S. The double-layered structure was transformed into AgSbS2 nanoparticles ~ 40 nm in diameter, after post-deposition heating at 350 °C. The AgSbS2-sensitized TiO2 electrodes were fabricated into liquid-junction solar cells. The best cell yielded a power conversion efficiency of 0.34% at 1 sun and 0.42% at 0.1 sun. The external quantum efficiency (EQE) spectrum covered the range of 380–680 nm with a maximal EQE of 10.5% at λ = 470 nm. The method can be applied to grow other systems of ternary semiconductor nanoparticles for solar absorbers. A redox shuttle to facilitate oxygen reduction in the lithium air battery Electrochemistry Communications, 26, January 2013, 74-76 Matthew J. Lacey, James T. Frith, John R. Owen A novel design of the non-aqueous lithium air cell is presented with a demonstration of a new reaction concept, involving a soluble redox shuttle to catalyse oxygen reduction. In principle, this can relieve the requirement for fast diffusion of molecular oxygen from the air interface to the positive electrode. To demonstrate this concept, ethyl viologen ditriflate was dissolved in BMPTFSI, reduced at a carbon electrode and regenerated by aspiration with oxygen. Useful shuttle behaviour, confirmed by several reduction–oxidation cycles, was observed in the case where the electrolyte contained at least 0.3 M lithium salt. The beneficial effect of the salt was attributed to its critical role in converting superoxide, which would otherwise destroy the shuttle, into the more desirable product of oxygen reduction, lithium peroxide. Steam gasification of plant biomass using molten carbonate salts Energy, 49, 1 January 2013, 211-217 Brandon J. Hathaway, Masanori Honda, David B. Kittelson, Jane H. Davidson This paper explores the use of molten alkali-carbonate salts as a reaction and heat transfer medium for steam gasification of plant biomass with the objectives of enhanced heat transfer, faster kinetics, and increased thermal capacitance compared to gasification in an inert gas. The intended application is a solar process in which concentrated solar radiation is the sole source of heat to drive ___________________________________________________________________________ page 210 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS the endothermic production of synthesis gas. The benefits of gasification in a molten ternary blend of lithium, potassium, and sodium carbonate salts is demonstrated for cellulose, switchgrass, a blend of perennial plants, and corn stover through measurements of reaction rate and product composition in an electrically heated reactor. The feedstocks are gasified with steam at 1200 K in argon and in the molten salt. The use of molten salt increases the total useful syngas production by up to 25%, and increases the reactivity index by as much as 490%. Secondary products, in the form of condensable tar, are reduced by 77%. Alkylation using an ionic liquid Focus on Catalysts, 2013, Issue 1, January 2013, 7 No abstract is available for this article. Ionic Liquids in Biotransformations and Organocatalysis Focus on Catalysts, 2013, Issue 1, January 2013, 8 Corrosion of superheater materials in a waste-to-energy plant Fuel Processing Technology, 105, January 2013, 106-112 Peter Viklund, Anders Hjörnhede, Pamela Henderson, Annika Stålenheim, Rachel Pettersson A major drawback when generating electricity from waste-fired boilers is the rapid corrosion of critical components such as superheater tubes. In this work a number of commonly-used superheater materials have been exposed on internally cooled probes in a waste-fired grate boiler. The investigated materials are the ferritic steel 13CrMo44, the ferritic–martensitic steel HCM12A, the austenitic steels Super 304, 317L and Sanicro 28, and the nickel-base alloys Hastelloy C-2000 and Inconel 625. Short-term exposures (3 h) for analysis of deposit composition and initial corrosion, as well as long-term exposures (1550 h) to investigate corrosion rates and corrosion characteristics have been made. Analysis revealed a deposit dominated by CaSO4, KCl and NaCl, but also appreciable amounts of low melting salt mixtures such as ZnCl2–KCl, PbCl2– KCl, FeCl2–KCl and NaCl–NiCl2. Metal loss measurements showed unacceptably high corrosion rates for 13CrMo44, HCM12A and Super 304. The corrosion attack for these alloys was manifested by the formation of mixed metal chloride/metal oxide scales. A different type of behaviour was seen for the higher alloyed austenitic steels and nickel-base alloys, which were able to form a chromium-enriched oxide next to the metal. However, these alloys suffered from some localised pitting attack. The behaviour is explained by oxide dissolution in the molten salts that are present in the deposit. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 211 PUBLICATIONS Towards a comprehensive thermodynamic database for ash-forming elements in biomass and waste combustion — Current situation and future developments Fuel Processing Technology, 105, January 2013, 129-141 Daniel Lindberg, Rainer Backman, Patrice Chartrand, Mikko Hupa Thermodynamic modeling is used as a tool to predict the chemistry of ashforming elements in biomass and waste combustion for corrosion- or depositionrelated issues. One major limitation is the lack of comprehensive databases that contain the thermodynamic data of ash compounds and phases formed during combustion. The present paper is a review of the state-of-the-art of the thermodynamic models and databases for ashes of biomass and waste combustion, future developments and the coupling of thermodynamic modeling with modeling of physical properties of molten ash. Recent developments have improved the accuracy for predicting the phase equilibria of alkali salt mixtures. The databases are being expanded by taking into account Ca, Pb, and Zn in the salt mixtures. Chromates have also been included to predict the stabilities of the corrosion products on boiler heat exchanger materials. The thermodynamic data for silicate systems still lack data for critical subsystems for biomass ashes. The K2O–CaO–SiO2 system which is important for slagging and agglomeration in biomass combustion still needs experimental investigations to make accurate modeling possible. The thermodynamic data of phosphates are discussed and a new modeling approach for molten phosphates is shown for the K2O–P2O5 system. Models for predicting physical properties coupled with the thermodynamic functions of molten silicates and salts are reviewed. Examples of advanced thermodynamic modeling to study ash-related issues in biomass combustion are also shown. Effect of pretreatment temperature on the yield and properties of bio-oils obtained from the auger pyrolysis of Douglas fir wood Fuel, 103, January 2013, 672-682 Shi-Shen Liaw, Shuai Zhou, Hongwei Wu, Manuel Garcia-Perez This paper investigates the effect of thermal pretreatment temperatures between 200 and 370 °C on the yield and composition of products (bio-charm gasm water and organics) obtained when Douglas-fir wood was subsequently pyrolyzed in an auger reactor at 500 °C. The yield of products was reported for the pretreatment and pyrolysis steps separately, and for the two steps added. The maximum yield of bio-oils achieved without pretreatment was close to 59 mass%. A decrease in total liquid yield was observed when the biomass was pretreated at 300 °C. At higher temperatures, the yields of Douglas-fir primary degradation products (lignin oligomers, anhydrosugars and alkylated and methoxylated phenols) decreased. The overall water yield increased gradually to 14 mass% at a pretreatment temperature of 290 °C. The yield of lignin oligomers also decreased as the pretreatment temperature increased. A drastic ___________________________________________________________________________ page 212 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS reduction in the yield of methoxylated phenols derived from guaiacyl (G) was observed when the biomass was pretreated at temperatures over 300 °C. This drastic reduction in the yield of methoxylated lignin derivatives can be explained by the formation of liquid intermediates that facilitate the formation of ionic species, enhancing dehydration reactions leading to the production of oquinone methide intermediates critical for bio-char formation. Torrefaction of ionic-liquid impregnated lignocellulosic biomass and its comparison to dry torrefaction Fuel, 103, January 2013, 814-826 A. Sarvaramini, O. Gravel, F. Larachi Torrefaction of woody biomass as a thermal pretreatment to increase biomass energy density is prerequisite to many thermochemical conversions. An ionicliquid (IL) biomass torrefaction route was proposed and investigated as an alternative to conventional dry and wet torrefaction for enhancing the rate of biomass torrefaction and for potentially improving the quality of torrefied solid products. Ionic liquid-impregnated aspen, birch and sawdust were torrefied in the 240–280 °C temperature range using [Emim][OTf], [Emim][BF4] and [Hmim][NTf2] ILs. To assess the benefits of IL impregnated biomass, dry and IL torrefaction were compared in terms of mass yield, energy density, energy yield, hydrophobicity and ultimate moisture uptake of torrefied solid products using thermogravimetry and fixed-bed setups. At equal reaction time and treatment temperature, the decomposition rates of birch, aspen and sawdust in ILs were considerably enhanced compared to their dry torrefaction counterparts. IL torrefaction led to increased energy density of treated aspen, birch and sawdust solids alike, whereas improved hydrophobicity of IL-torrefied solids translated in nearly 40–45% reduction of their ultimate moisture uptake. Finally, char and ash leftovers building up in spent ILs after repeated IL torrefaction cycles were specifically addressed as potential factors responsible for IL decomposition. Fast oxidative desulfurization of fuel oil using dialkylpyridinium tetrachloroferrates ionic liquids Fuel, 103, January 2013, 997-1002 Yi Nie, Yuxiao Dong, Lu Bai, Haifeng Dong, Xiangping Zhang , In this work, a series of Lewis acidic ionic liquids (ILs), dialkylpyridinium tetrachloroferrates [C43MPy]FeCl4, [C83MPy] FeCl4, and [C83MPy] FeCl4 ), was synthesized and utilized as extractant and catalyst to investigate the oxidative removal of dibenzothiophene (DBT) from model oil, with 30 wt% hydrogen peroxide (H2O2) solution as oxidant. The effects of reaction time, temperature, H2O2/DBT molar ratio, initial sulfur content, IL/oil mass ratio, and alkyl chain length of IL cation ring on the DBT removal of model oil were investigated in detail. Dialkylpyridinium tetrachloroferrates ILs presented good catalytic ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 213 PUBLICATIONS activity and high extraction performance on the desulfurization of model oil, with the advantages of fast reaction equilibrium, high sulfur removal of 100%, low temperature, and low mass ratio of IL/oil. The desulfurization system could be recycled twice without a significant decrease in desulfurization activity. Kinetics of oxidative desulfurization of DBT by H2O2 and [C43MPy] FeCl4 is first-order with an apparent rate constant of 0.9951 min−1 at 1/3 IL/oil mass ratio and 298 K. [C83MPy] FeCl4 can reduce sulfur content in actual gasoline from 468 ppm to 261 ppm with a sulfur removal of 44% at IL/gasoline mass ratio of 1/3. The present work shows that fuel oil can be purified into ultralow sulfur fuels through further deep oxidative desulfurization using acidic ILs after hydrodesulfurization. Preparation of ultrafine tungsten wire via electrochemical method in an ionic liquid Fusion Engineering and Design, 88, Issue 1, January 2013, 23-27 Xueqi Gao, Wencheng Hu, Yushu Gao Ultrafine tungsten wire less than 10 µm in diameter is often used as wire array load applied in Inertial Confinement Fusion (ICF) physical experiments. In order to obtain a higher yield of X-ray, both initial radius and line quality of metal wire were required to be of high quality simultaneously. This paper has studied the electrochemical method to corrode tungsten wires uniformly in an ionic liquid electrolyte containing 1 wt% sodium hydroxide. A three electrode system composed of a tungsten anode electrode, a stainless steel cathode and a saturated calomel electrode as a reference electrode, was used in the electrochemical experiments. Liner sweep voltammetry (LSV) and Tafel experiments were used to investigate the electrochemical behaviors of tungsten wires in ionic liquid and aqueous solution. Based on scanning electron microscope (SEM) observation, the morphologies of tungsten wire surface with uniform corrosion under different applied voltages have been demonstrated. Xray diffraction (XRD) methods were employed to track the evolution of the crystal structure before and after corrosions, and there is an obvious difference in peak intensities. The ultrafine tungsten wire with a uniform diameter of 8.5 µm was obtained under the optimized electric potential (2.5 V) applied for decreasing diameter at 30 °C. Chapter 11.1.8 - Sonoprocess of Ceramic Materials Handbook of Advanced Ceramics (Second Edition), 2013, 1001-1010 Naoya Enomoto Application of power ultrasound to ceramic materials processing has been reviewed. After the historical background and the physicochemical basis of ultrasound are explained, the apparatus and the power determination for sonoprocess are noticed for the readers to execute a sonochemical experiment properly. Case studies of ceramic sonoprocessing are briefly and variously ___________________________________________________________________________ page 214 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS introduced with 36 references quoted. They involve the ultrasonic effects on dissolution and precipitation (ripening of aluminogel), nucleation and growth of alum crystals from a supersaturated solution, oxidation (Fe2+/Fe3+, magnetite etc.), reduction (noble metal nanoparticles, Au, Pt, Ag, etc.), polymerization (nanocarbon etc.), sol-gel process using metal alkoxides, electrochemical process, and solidification of molten salt. Chapter 254 - Lanthanidomesogens Handbook on the Physics and Chemistry of Rare Earths, 43, 2013, 1-158 Koen Binnemans Lanthanidomesogens can be defined as liquid-crystalline lanthanide complexes or lanthanide-containing liquid crystals. These compounds combine the unique properties of lanthanide ions (luminescence, paramagnetism) with those of liquid crystals (fluidity, anisotropy, response to electrical and magnetic fields). Lanthanidomesogens allow obtaining materials that emit linearly polarized light or that can be aligned by an external magnetic field. This Chapter gives a detailed discussion of the different classes of lanthanidomesogens, including Schiff’s base complexes, beta-diketonates, beta-enaminoketonates, bis(benzimidazolyl)pyridine complexes, phthalocyanines, porphyrins, lanthanide soaps, polyoxometalatate-surfactant complexes, ionic liquid-crystalline lanthanide complexes and lyotropic lanthanidomesogens. Also an overview of actinide-containing liquid crystals (actinidomesogens) is given. The reader is introduced to the different types of mesophases and to the experimental methods used for identification of these mesophases. Chapter 255 - Recycling of Rare Earths from Scrap Handbook on the Physics and Chemistry of Rare Earths, 43, 2013, 159-211 Mikiya Tanaka, Tatsuya Oki, Kazuya Koyama, Hirokazu Narita, Tetsuo Oishi With the increased concern about the rare-earth supply chain risk, recycling rare-earths from scrap is receiving significant attention. In this monograph, the studies of the rare-earth recycling technologies have been reviewed with respect to magnets, phosphors, batteries, polishing powders and others from the viewpoints of physical separation, hydrometallurgy, and pyrometallurgy. The important issues inherent in each scrap were pointed out. Particularly-important issues are dismantling, demagnetization, the separation from iron for the magnets, and the fine particle separation and the terbium dissolution for the phosphors. Emerging technologies, such as the automated dismantling methods for the magneta and the application of high gradient magnetic separation for the phosphors, together with a new extractant have been noted. A cost barrier before the actual implementation of the developed process should be overcome not ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 215 PUBLICATIONS only by the technologies, but also by the integration with a social system establishment. Chapter 256 - Ionic Liquids: New Hopes for Efficient Lanthanide/Actinide Extraction and Separation? Handbook on the Physics and Chemistry of Rare Earths, 43, 2013, 213-273 Isabelle Billard Ionic Liquids are of great interest in all fields of chemistry and material science. Apart from their “green” properties, their radioresistance and fantastic chemical versatility offer a new playground to nuclear chemists and others in view of liquid/liquid extraction of RE and actinides. Following a brief summary of RE and An liquid/liquid extraction by use of molecular solvents, the author reviews and discusses the main properties of ionic liquids that are of importance to liquid/liquid extraction. Then, the various ways ionic liquids are used for the extraction/separation of RE and An are critically reviewed and discussed. Focus is on mechanism and highlight is put on differences between ionic liquids and molecular solvents. Current status and development of membranes for CO2/CH4 separation: A review Review Article International Journal of Greenhouse Gas Control, 12, January 2013, 84-107 Yuan Zhang, Jaka Sunarso, Shaomin Liu, Rong Wang Carbon dioxide (CO2) is a greenhouse gas found primarily as a main combustion product of fossil fuel as well as a component in natural gas, biogas and landfill gas. The interest to remove CO2 from those gas streams to obtain fuel with enhanced energy content and prevent corrosion problems in the gas transportation system, in addition to CO2 implications to the climate change, has driven the development of CO2 separation process technology. One type of technology which has experienced substantial growth, breakthroughs and advances during past decades is membrane-based technology. The attractive features offered by this technology include high energy efficiency, simplicity in design and construction of membrane modules and environmental compatibility. The objective of this review is to overview the different types of membranes available for use including their working principles, current status and development which form the primary determinants of separation performance and efficiency. The emphasis is toward CO2/CH4 separation, considering its substantial and direct relevance to the gas industry. To this end, discussion is made to cover polymeric gas permeation membranes; CO2-selective facilitated transport membranes, hollow fiber gas–liquid membrane contactors, inorganic membranes and mixed matrix membranes. ___________________________________________________________________________ page 216 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS The market for CO2 separation is currently dominated by polymeric membranes due to their relatively low manufacturing cost and processing ability into flat sheet and hollow fiber configurations as well as well-documented research studies. While there have been immensely successful membrane preparation and development techniques with consequential remarkable performance for each type of membrane. Each type of membrane brings associated advantages and drawbacks related to the characteristic transport mechanism for specific application conditions. Inorganic membranes, for example, are very suitable for high temperature CO2 separation in excess of 400 °C while all other membranes can be applied at lower temperatures. The recent emergence of mixed matrix membranes has allowed the innovative approach to combine the advantages offered by inorganic and polymeric materials. Steric-effect-induced alteration of thermal transport phenomenon for mixed electroosmotic and pressure driven flows through narrow confinements International Journal of Heat and Mass Transfer, 56, Issues 1–2, 1 January 2013, 251-262 Ranabir Dey, Tanmay Ghonge, Suman Chakraborty The present paper addresses, for the first time, the thermal transport process for mixed electroosmotic and pressure-drive flows of electrolyte solutions, through nanoscopic confinements with step-change in the wall temperature, by going beyond the prevalent simplifying assumption of non-interacting, point charge behaviour of the ions in the electrolyte solution. An attempt is made here to delineate the alterations in the heat transfer characteristics induced by the inclusion of the finite ionic size effect or the ‘steric effect’, in the electrokinetic framework, which becomes very significant for electro-hydrodynamic flows through narrow-confinements with high surface charge density. Under such situations the finite size of the ions cannot be trivially precluded from the analysis, thereby rendering the point charge assumption erroneous. The distinctive influence of the ‘steric’ effect of ions on the heat transfer characteristics is numerically investigated by delineating the variations in the local liquid temperature, local Nusselt number and the thermal entrance length for the thermally developing regime. The observed significant influences of the bulk fraction of ions, as represented by the steric factor, on the thermal transport phenomenon are physically explained by simultaneously highlighting their intrinsic differences with the effects of other existing parameters, like Joule heating and viscous dissipation. The utilitarian scope of the work lies in the fact that it proposes a more comprehensive methodology for analyzing the heat transfer characteristics in state-of-the-art nanoscale electromechanical devices. Vortex-assisted ionic liquid microextraction coupled to flame atomic ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 217 PUBLICATIONS absorption spectrometry for determination of trace levels of cadmium in real samples Journal of Advanced Research, 4, Issue 1, January 2013, 35-41 Mahmoud Chamsaz, Atefe Atarodi, Mohammad Eftekhari, Saeid Asadpour, Mina Adibi A simple and rapid vortex assisted ionic liquid based liquid–liquid microextraction technique (VALLME) was proposed for preconcentration of trace levels of cadmium. According to this method, the extraction solvent was dispersed into the aqueous samples by the assistance of vortex agitator. Cadmium preconcentration was mediated by chelation with the 8hydroxyquinoline (oxine) reagent and an IL, 1-octyl-3-methylimidazolium hexafluorophosphate ([Omim][PF6]) was chosen as the extraction solvent to extract the hydrophobic complex. Several variables such as sample pH, concentration of oxine, of [Omim][PF6] and extraction time were investigated in details and optimum conditions were selected. Under the optimum conditions, the limit of detection (LOD) was 2.9 µg L−1 for Cd (ІІ) and relative standard deviation (RSD%) for five replicate determinations of 125 µg L−1 was 4.1%. The method was successfully applied to the determination of cadmium in tap water, apple and rice samples. Removal of imidazolium ionic liquids by microbial associations: Study of the biodegradability and kinetics Journal of Bioscience and Bioengineering, 115, Issue 1, January 2013, 71-75 Ewa Liwarska-Bizukojc, Dorota Gendaszewska The aim of this study was to estimate the biodegradability of the selected imidazolium ionic liquids and to determine the kinetic parameters for the biological treatment of wastewater containing these ionic liquids. Biodegradability was evaluated with the help of the Organisation for Economic Co-operation and Development (OECD) tests, while oxygen uptake rate (OUR) tests were made in order to calculate the values of Monod kinetic parameters. The results obtained from both types of the tests showed that ionic liquids of chemical structure of 1-alkyl-3-methyl imidazolium bromide were poorly biodegradable and co-biodegradable compounds, although their biodegradability increased with the elongation of the alkyl chain length. At the same time the presence of the imidazolium-based ionic liquids in wastewater at concentration of 50 mg l−1 did not inhibit biomass growth as well as did not decrease the affinity of substrate to biomass. The values of both Monod kinetic parameters, i.e., maximum specific growth rate (µmax) and half saturation constant (KS), increased with the increase in chain length of the alkyl substituent. Ionic-liquid-catalyzed decarboxylation of glycerol carbonate to glycidol ___________________________________________________________________________ page 218 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Journal of Catalysis, 297, January 2013, 248-255 Ji Sik Choi, Fidelis Stefanus Hubertson Simanjuntaka, Ji Young Oh, Keun Im Lee, Sang Deuk Lee, Minserk Cheong, Hoon Sik Kim, Hyunjoo Lee Decarboxylation of glycerol carbonate (GLC) to produce 2,3-epoxy-1-propanol (glycidol) was conducted using various kinds of ionic liquids (ILs) as catalysts. ILs bearing an anion with medium hydrogen-bond basicity such as and I− exhibited the higher glycidol yields than those having an anion with low or strong hydrogen-bond. FT-IR spectroscopic analysis shows that both GLC and glycidol interact with anions of ILs through their hydroxyl groups. It was possible to improve the yield of glycidol when a zinc salt with a medium Lewis acidity was co-present along with an IL. The yield of glycidol was greatly increased up to 98% when the decarboxylation was conducted in the presence of a high-boiling aprotic solvent. Computational calculations on the mechanism using 1-butyl-3-methylimidazolium nitrate as a catalyst revealed that the first step is the -assisted ring-opening of GLC followed by the ring closure, resulting in the formation of a 3-membered ring intermediate species. A comparative study of anodic oxidation of bromide and chloride ions on platinum electrodes in 1-butyl-3-methylimidazolium hexafluorophosphate Journal of Electroanalytical Chemistry, 688, 1 January 2013, 371-378 Linpo Yu, Xianbo Jin, George Z. Chen The anodic processes of bromide and chloride ions on platinum electrodes were investigated in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, under the same conditions. The halide anions were added to the ionic liquid as their 1-butyl-3-metylimidazolium salts or tetrabutylammonium salts to high concentrations (up to 1.1 mol L−1). Analysis and comparison of the electrode reactions were made through cyclic voltammetry, chronoamperometry, and double potential step chronocoulometry with a platinum micro-disk electrode, and bulk potentiostatic electrolysis and UV–Vis spectroscopy. Both halide anions exhibited anodic oxidation. The main difference as revealed by cyclic voltammetry was that the chloride ion exhibited only one anodic current peak, whilst the bromide ion underwent clearly distinguished two oxidation steps. This difference is attributed to different electrode kinetics and stabilities of the two tri-halide ions. Bulk electrolysis and UV–Vis spectroscopy confirmed that the tri-bromide ion was the main product from the overall oxidation of the bromide ion, although bromine formation was indicated by cyclic voltammetry at potentials of the second anodic peak. Lithium ion battery separators: Development and performance characterization of a composite membrane Journal of Membrane Science, Volumes 425–426, 1 January 2013, 163-168 ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 219 PUBLICATIONS Xiaosong Huang, Jonathon Hitt The overall stability of the lithium ion battery separators, under potentially extreme battery operating conditions, will require leading edge design and fabrication techniques to exceed manufacturing and end performance requirements for large scale applications. This paper features the development and performance characterization of an inorganic fiber enhanced composite separator for LIBs. This composite separator can offer a thermally stable alternative for conventional porous polyolefin separators, which shrink significantly at high temperatures. The relative affinities between the electrolyte and the submicron inorganic fibers and the electrolyte and the polyvinylidene fluoride binder ensured a superior wettability of the final separator by the liquid electrolyte. The high porosity and the open porous structure of the composite separator resulted in a good effective ionic conductivity. Coin cells with this composite separator also exhibited stable cycle performance and improved rate capabilities, especially when discharged at rates greater than C/2. Methyltrioxorhenium-catalyzed epoxidation of olefins with hydrogen peroxide as an oxidant and pyridine N-oxide ionic liquids as additives Journal of Molecular Catalysis A: Chemical, 366, January 2013, 149-155 Yuecheng Zhang, Zhaozhao Li, Xiaohui Cao, Jiquan Zhao Four ionic liquids (ILs) with both a pyridine N-oxide moiety and an imidazolium moiety combined by an amide spacer were synthesized through a series of reactions including amidation, peroxidation, quaterization and anion exchange reaction. Their structures were fully characterized by 1H NMR, FT-IR, UV–vis and HR–MS. The ionic liquids were used respectively as additives in the methyltrioxorhenium (MTO) catalyzed epoxidation of olefins with 30% H2O2 as an oxidant. The catalytic results displayed that the ILs had excellent performances in suppressing epoxide ring-opening reaction, which led to the significant improvement of the selectivity of the MTO-catalyzed epoxidation with low loadings compared to other substances as additives. The coexistence of the pyridine N-oxide and imidazolium moieties in the structures of ILs is necessary in improving the MTO-catalyzed epoxidation reaction. It was also displayed that the improvement degree on the selectivity of epoxidation depended on the type of anion of the ILs, but not the position of the substituent with imidazolium moiety in the ring of pyridine N-oxide. Meanwhile, the results also showed that the introduction of the ILs caused the decrease of the epoxidation rate, but this side effect was small compared to those of other substances used as additives. Novel bi-SO3H-functionalized ionic liquids based on piperazinium: Highly efficient and recyclable catalysts for the synthesis of β-acetamido ketones ___________________________________________________________________________ page 220 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Journal of Molecular Catalysis A: Chemical, 366, January 2013, 195-201 Yuanyuan Wang, Junlong Zhou, Kun Liu, Liyi Dai A series of novel bi-SO3H-functionalized ionic liquids were synthesized and acted as catalysts for the synthesis of β-acetamido ketones. Compared with traditional single-SO3H-functionalized ionic liquids, less amount of catalysts, higher yields and shorter reaction time are the key features of this methodology. Hammett function values and the minimum-energy geometries of bi-SO3Hfunctionalized ILs were calculated and the results revealed that the acidities and catalytic activities of ILs in synthesis of β-acetamido ketones were influenced by their structures. The IL [(PS)2pi][OTf]2 with the shortest H—O bond distance had the strongest acidity and the highest catalytic activity. The effect of vinyl-containing ionic liquid on the photocatalytic activity of iron-doped TiO2 Journal of Molecular Catalysis A: Chemical, 366, January 2013, 222-227 Fang Deng, Xubiao Luo, Ke Li, Xinman Tu, Shenglian Luo, Lixia Yang, Ninghui Zhou, Hongying Shu Visible light responsive iron-doped TiO2 (Fe3+/TiO2-IL) was synthesized by sol– gel method using 1-vinyl-3-propylimidazolium iodide (VPIM+I−) as a reaction medium. VPIM+I− not only made the morphological and structural changes of Fe3+/TiO2-IL, but also extended its absorption edge to the visible light region. The photocatalytic activity of Fe3+/TiO2-IL was tested in the degradation of 2nitrophenol under simulated solar light irradiation. The photocatalytic activity of Fe3+/TiO2-IL was higher than the samples prepared in the reaction medium without VPIM+I−. Moreover, the effect of pH and H2O2 on the photocatalytic activity of Fe3+/TiO2-IL was also investigated. Fe3+/TiO2-IL showed high photocatalytic activity in acidic environment, and H2O2 had a dual effect on the photocatalytic activity Fe3+/TiO2-IL. Enhancements of enantio and diastereoselectivities in reduction of (Z)-3halo-4-phenyl-3-buten-2-one mediated by microorganisms in ionic liquid/water biphasic system Journal of Molecular Catalysis B: Enzymatic, Volumes 85–86, January 2013, 61-64 Dávila S. Zampieri, Bruno R.S. de Paula, Luiz A. Zampieri, Juliana A. Vale, J. Augusto R. Rodrigues, Paulo J.S. Moran (Z)-C6H5CH=CXC (=O)CH3 (X = Cl, Br) mediated by Saccharomyces cerevisiae, Candida albicans, Rhodotorula glutinis, Geotrichum candidum and Micrococcus luteus gave the corresponding halohydrins through consecutive reduction reactions of C=C and C=O bonds. In general, the reactions performed ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 221 PUBLICATIONS in the biphasic system water/[(bmim)PF6] gave better diastereoselectivity and enantioselectivity than in pure water. On the reactivity of the Melanocarpus albomyces laccase and formation of coniferyl alcohol dehydropolymer (DHP) in the presence of ionic liquid 1allyl-3-methylimidazolium chloride Journal of Molecular Catalysis B: Enzymatic, Volumes 85–86, January 2013, 169-177 Maarit Lahtinen, Liisa Viikari, Pirkko Karhunen, Janne Asikkala, Kristiina Kruus, Ilkka Kilpeläinen Some ionic liquids are able to dissolve wood, including lignin and lignocellulose, and thus they provide an efficient reaction media for modification of globally abundant wood-based polymers. Lignin can be modified with laccases (EC 1.10.3.2), multicopper oxidases, which selectively catalyze the oxidation of phenolic hydroxyl to the phenoxy radical in lignin by using oxygen as the co-substrate and an electron acceptor. Many enzymes, including laccases, retain their catalytic activity in the presence of ionic liquids. However, the enzyme activity is usually decreased in the presence of ionic liquids, and the most deactivating ionic liquids have been observed to be those dissolving wood most efficiently. In the present study the activity, pH optimum and catalyzed oxidation of coniferyl alcohol by the laccase from the ascomycete Melanocarpus albomyces was investigated in the ionic liquid 1-allyl-3-methylimidazolium chloride ([Amim]Cl), known to dissolve wood and expected to affect the laccase activity. Indeed, with an increasing concentration of [Amim]Cl, the activity of M. albomyces laccase decreased, and the pH range of the enzyme activity was narrowed. The pH optimum, using 2,6dimethoxyphenol as the substrate, was shifted from 6.5 to 6.0 when the amount of [Amim]Cl was increased to 60% (m-%). It was also found that the inhibition of laccase with NaN3 was not as severe in the ionic liquid as in water. The insoluble fraction of the dehydropolymer (DHP) formed in the presence of [Amim]Cl had clearly higher molecular weight compared to the one formed in water. DHPs formed in the absence and presence of [Amim]Cl both contained β5, β–β, β-O-4, α-C=O/β-O-4 and α-O-4/β-O-4 structures. However, in the presence of [Amim]Cl, less β-O-4, slightly less β-5 and more β–β structures were formed. Choline-based deep eutectic solvents for enzymatic preparation of biodiesel from soybean oil Journal of Molecular Catalysis B: Enzymatic, Volumes 85–86, January 2013, 243-247 Hua Zhao, Cheng Zhang, Tanisha D. Crittle ___________________________________________________________________________ page 222 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS In this study, we introduced choline-based deep eutectic solvents (such as choline chloride/glycerol at 1:2 molar ratio) as inexpensive, non-toxic, biodegradable and lipase-compatible solvents for the enzymatic preparation of biodiesel from soybean oil. Through the evaluation of different eutectic solvents and different lipases, as well as the study of reaction parameters (i.e. methanol concentration, Novozym 435 loading and reaction time), we were able to achieve up to 88% triglyceride conversions in 24 h. The enzyme could be reused for at least four times without losing much activity. Our results indicate that new benign eutectic solvents can be used as substitutes of toxic and volatile organic solvents in the enzymatic production of biodiesel from real triglycerides (such as soybean oil). Corrosion study of a highly durable electrolyzer based on cold crucible technique for pyrochemical reprocessing of spent nuclear oxide fuel Journal of Nuclear Materials, 432, Issues 1–3, January 2013, 35-41 M. Takeuchi, Y. Arai, T. Kase, Y. Nakajima The application of the cold crucible technique to a pyrochemical electrolyzer used in the oxide-electrowinning method, which is a method for the pyrochemical reprocessing of spent nuclear oxide fuel, is proposed as a means for improving corrosion resistance. The electrolyzer suffers from a severe corrosion environment consisting of molten salt and corrosive gas. In this study, corrosion tests for several metals in molten 2CsCl–NaCl at 923 K with purging chlorine gas were conducted under controlled material temperature conditions. The results revealed that the corrosion rates of several materials were significantly decreased by the material cooling effect. In particular, Hastelloy C22 showed excellent corrosion resistance with a corrosion rate of just under 0.01 mm/y in both molten salt and vapor phases by controlling the material surface at 473 K. Finally, an engineering-scale crucible composed of Hastelloy C-22 was manufactured to demonstrate the basic function of the cold crucible. The cold crucible induction melting system with the new concept Hastelloy crucible showed good compatibility with respect to its heating and cooling performances. Application of a boron doped diamond (BDD) electrode as an anode for the electrolytic reduction of UO2 in Li2O–LiCl–KCl molten salt Journal of Nuclear Materials, 432, Issues 1–3, January 2013, 175-181 Wooshin Park, Jong-Kook Kim, Jin-Mok Hur, Eun-Young Choi, Hun Suk Im, Sun-Seok Hong A boron doped diamond thin film electrode was employed as an inert anode to replace a platinum electrode in a conventional electrolytic reduction process for UO2 reduction in Li2O–LiCl molten salt at 650 °C. The molten salt was changed ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 223 PUBLICATIONS into Li2O–LiCl–KCl to decrease the operation temperature to 550 °C at which the boron doped diamond was chemically stable. The potential for oxygen evolution on the boron doped diamond electrode was determined to be approximately 2.2 V vs. a Li–Pb reference electrode whereas that for Li deposition was around −0.58 V. The density of the anodic current was low compared to that of the cathodic current. Thus the potential of the cathode might not reach the potential for Li deposition if the surface area of the cathode is too wide compared to that of the anode. Therefore, the ratio of the surface areas of the cathode and anode should be precisely controlled. Because the reduction of UO2 is dependent on the reaction with Li, the deposition of Li is a prerequisite in the reduction process. In a consecutive reduction run, it was proved that the boron doped diamond could be employed as an inert anode. Cerium and neodymium co-precipitation in molten chloride by wet argon sparging Journal of Nuclear Materials, 432, Issues 1–3, January 2013, 407-413 J.F. Vigier, C. Renard, A. Laplace, J. Lacquement, F. Abraham Co-precipitations of cerium (III) and neodymium (III) at 10 wt.% in LiCl–CaCl2 (30-70 mol%) molten salt at 705 °C have been achieved using an original way of precipitation, wet argon sparging. Several CeCl3/NdCl3 ratios have been studied, and the isolated powders were analyzed using different characterization methods including XRD investigations. The lanthanides precipitation yields have been determined around 99.9% using ICP-AES analysis. XRD demonstrated that the precipitates mainly contained mixed oxychloride (Ce1−xNdx)OCl and a small amount of the mixed oxide Ce1−yNdyO2−0.5y. Calcination of these precipitates has resulted in the cerium and neodymium mixed oxides. For the precipitation with a Ce/Nd = 50/50 ratio, an hydroxychloride Ln(OH)2Cl and the oxychloride CeIV(Nd0.7Ce0.3)IIIO3Cl have been identified as unexpected intermediate compounds. Hybrid macroporous Pd catalytic discs for 4-nitroaniline hydrogenation: Contribution of the alginate-tetraalkylphosphonium ionic liquid support Journal of Organometallic Chemistry, 723, 1 January 2013, 90-97 T. Vincent, P. Krys, C. Jouannin, A.-C. Gaumont, I. Dez, E. Guibal Tetraalkylphosphonium ionic liquid (IL) was immobilized in a composite material made of alginate and cellulose fibers (to strengthen the gel) conditioned under the form of highly porous discs. These materials have been used for immobilizing Pd(II) by adsorption from HCl solutions. The metal reduction allows to prepare a catalytic material that was successfully used for the hydrogenation of 4-nitroaniline into p-phenylenediamine using formic acid as the hydrogen donor. The main objective of the study is to understand the contribution of the IL in the catalytic activity. The hydrogenation kinetics were ___________________________________________________________________________ page 224 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS compared for raw material (containing the IL) and for methanol-washed material (without IL) for 8 successive catalytic runs. The presence of the IL allows to stabilize Pd micro/nanoparticles and prevents their release to the solution. Development and efficient 1-glycyl-3-methyl imidazolium chloride– copper(II) complex catalyzed highly enantioselective synthesis of 3, 4dihydropyrimidin-2(1H)-ones Journal of Organometallic Chemistry, 723, 1 January 2013, 154-162 Parasuraman Karthikeyan, Sachin Arunrao Aswar, Prashant Narayan Muskawar, Pundlik Rambhau Bhagat, S. Senthil Kumar A novel, effective asymmetric 1-glycyl-3-methyl imidazolium chloridecopper(II) complex [[Gmim]Cl–Cu(II)] was synthesized and studied as organocatalyst for enantioselective Biginelli reaction under solvent free condition at 25°C. The hydrophobic group on amino acid favors reagent diffusion towards the chloroglycine moiety increasing the catalytic activity of supported palladium complex. Spectroscopic evidence of complex has been proved by Powder XRD, SEM, FT-IR and AFM. This method contains simplified product isolation and catalyst recycling, affording substituted aldehydes imparting high yield with excellent stereoselectivity. This recyclable heterogeneous catalyst provides a simple strategy for the generation of a variety of new C–C bonds under environmentally benign condition. Copper(I)-catalyzed tandem reaction of 2-iodophenols with isothiocyanates in room temperature ionic liquids Journal of Organometallic Chemistry, 723, 1 January 2013, 137-142 Fang Yao, Wenyan Hao, Ming-Zhong Cai A copper(I)-catalyzed tandem reaction of 2-iodophenols with isothiocyanates in hydrophobic [bmim][PF6] ionic liquid was described, which proceeded smoothly and generated a variety of 2-iminobenzo-1,3-oxathioles in good to excellent yields. The tandem reaction that was carried out in [bmim][PF6] has some obvious advantages such as reaction rate acceleration and yield increasing as compared with the reaction run in volatile solvents such as toluene. Furthermore, the CuI/1,10-phenanthroline catalytic system can be reused up to 6 times without loss of activity and efficiency. Ionothermal synthesis of uranyl compounds that incorporate imidazole derivatives Journal of Solid State Chemistry, 197, January 2013, 266-272 Ernest M. Wylie, Megan K. Dustin, Jeremy S. Smith, Peter C. Burns ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 225 PUBLICATIONS Ionothermal reactions of uranyl nitrate with various salts in methylimidazoliumbased ionic liquids have produced single crystals of three uranyl compounds that incorporate imidazole derivatives as charge-balancing cations. (C4H7N2)[(UO2)(PO3F)(F)] (1) crystallizes in space group C2, a=17.952(1) Å, b=6.9646(6) Å, c=8.5062(7) Å, β=112.301(1)°, (C6H11N2)2[(UO2)(SO4)2] (2) crystallizes in space group C2/c, a=31.90(1) Å, b=9.383(5) Å, c=13.770(7) Å, β=93.999(7)° and (C6H11N2)[(UO2)2(PO4)(HPO4) (3) crystallizes in space group P21/n, a=9.307(2), b=18.067(4), c=9.765(2), β=93.171(2). The U6+ cations are present as (UO2)2+ uranyl ions coordinated by three O atoms and two F atoms in 1 and five O atoms in 2 and 3 to give pentagonal bipyramids. The structural unit in 1 is composed of F-sharing dimers of uranyl pentagonal bipyramids linked into sheets through corner-sharing fluorophosphate tetrahedra. The structural unit in 2 is composed of uranyl pentagonal bipyramids with one chelating sulfate tetrahedron linked into chains by three other corner-sharing sulfate tetrahedra. In 3, the structural unit is composed of chains of uranyl pentagonal bipyramids linked into sheets through edge- and corner-sharing phosphate and hydrogen phosphate tetrahedra. N-methylimidazolium cations occupy the interstitial space between the uranyl fluorophosphate sheets in 1, whereas 1-ethyl-3methylimidazolium cations link the uranyl sulfate and phosphate units in 2 and 3 into extended structures. Chapter 4 - Secondary Chemical Equilibria in Reversed-Phase Liquid Chromatography Liquid Chromatography, 2013, 87-104 M.C. García-Álvarez-Coque, J.R. Torres-Lapasió The addition of reagents to an RPLC mobile phase enables the separation of ionizable compounds, inorganic anions, and metal ions using conventional instrumentation, silica-based materials, and hydro-organic mixtures, thanks to a variety of secondary equilibria. This gives rise to several chromatographic modes, whose main features are outlined in this chapter. The effect of the mobile phase pH on the retention of ionizable compounds is described, together with the recommended experimental practice. The mechanism of adsorption of amphiphilic anions or cations on the stationary phase to attract analytes with opposite charge or suppress the silanol activity is discussed. Different reagents, such as alkylammonium salts, surfactants (below and above the critical micelle concentration), perfluorinated carboxylate anions, chaotropic ions, and ionic liquids, are considered. The potential of metal chelation for the determination of metal ions and organic compounds is also summarized. Chapter 7 - Liquid–Solid Chromatography Liquid Chromatography, 2013, 143-156 L.R. Snyder, J.W. Dolan ___________________________________________________________________________ page 226 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Liquid-solid or normal-phase chromatography is employed for the separation of non-ionic solutes by adsorption onto the surface of an inorganic oxide stationary phase and displacement by competition with the components of the mobile phase. It has particular advantages for compound-class separations and the separation of diasteromers and geometrical isomers soluble in organic solvents. Common stationary phases for high-performance liquid chromatography include silica and chemically-bonded silica phases with 3-cyanopropyl, 3-aminopropyl, and spacer bonded propanediol groups. The use of eluotropic series for mobile phase selection are described as well as general strategies for method development. Selective electrodes for [PF6]− and [BF4]− anions based on the associates formed by ionic liquid and cationic dyes Materials Science and Engineering: C, 33, Issue 1, 1 January 2013, 356-361 Zhenning Yan, Yuanchao Pei, Jing Fan, Shuangqiang Wang, Jianji Wang The feasibility of the newly synthesized ionic associates L1 and L2 formed by ionic liquid [C4mim][PF6] and cationic dyes (malachite green and methylene blue) has been tested as a novel ionophore for the preparation of anion-selective polymeric membrane electrodes. The electrode exhibits Nernstian response and enhanced potentiometric selectivity towards [PF6]− compared to many other anions. The influence of some experimental parameters such as membrane composition, nature of plasticizer and amount of additive on the potential response of the [PF6]− sensor are investigated. Under the optimized conditions, the response slopes of the membrane electrodes towards [PF6]− are 59.7 ± 0.5 and 58.1 ± 0.5 mV/decade based on ionophore L1 and L2, respectively, in 1.0 × 10− 5–1.0 × 10− 1 or 1.0 × 10− 6–1.0 × 10− 1 mol/L concentration range. Interestingly, the optimized electrodes based on ionophores L1 and L2 also exhibit Nernstian response characteristics (60.3 ± 0.5 and 56.0 ± 0.5 mV/decade) for tetrafluoroborate anion [BF4]− in a wide concentration range. Thus, the proposed sensor has been used for the determination of [PF6]− and [BF4]− in aqueous ionic liquids samples and the solubility of the [PF6]− and [BF4]− based ionic liquids in water. The satisfactory results are obtained. Chapter 10 - Chemical Applications Micro-Drops and Digital Microfluidics (Second Edition), 2013, 387-420 Jean Berthier Chapter 10 is devoted to the study of the behavior of chemical components on EWOD-based chips, especially of organic solvents and ionic liquids. The maneuverability of these different liquids on the substrate of a microsystem is analyzed, and it is shown how these carrier fluids can be used to realize controlled chemical reactions in microdrops. ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 227 PUBLICATIONS Dispersive micro-solid phase extraction with ionic liquid-modified silica for the determination of organophosphate pesticides in water by ultra performance liquid chromatography Microchemical Journal, 106, January 2013, 311-317 Francisco Galán-Cano, Rafael Lucena, Soledad Cárdenas, Miguel Valcárcel In this article, the use of methylimidazolium-hexafluorophosphate functionalized silica is evaluated under a dispersive micro-solid phase extraction (D-µSPE) approach for the extraction of organophosphate pesticides (OPs) from water samples. After its synthesis, the sorbent is chemically characterized playing special attention to the type of interaction that it can establish with the target analytes. Moreover, different dispersion approaches were evaluated in order to clarify the main parameters affecting the extraction. The ionic liquidmodified silica allows the isolation and preconcentration of the analytes (phosmet, parathion, triazophos and phoxim) with enrichment factors in the range from 74 (phoxim) to 111 (triazophos) in a simple procedure. The new extraction mode allows the determination of these compounds with limits of detection in the range from 0.3 µg L− 1 (for phosmet) to 0.6 µg L− 1 (for phoxim) with a relative standard deviation lower than 10.6% (for phoxim). The recovery study carried out in different water samples provided an average recovery of 94%, which demonstrated the applicability of the sorbent for the analytical problem selected in this article. Highly luminescent yellow and yellowish-green light-emitting electrochemical cells based on cationic iridium complexes with phenanthroline based ancillary ligands Optical Materials, 35, Issue 3, January 2013, 407-413 Chozhidakath Damodharan Sunesh, Midhun Chandran, George Mathai, Youngson Choe Highly luminescent light-emitting electrochemical cells (LECs) based on cationic iridium complexes [Ir(ppz)2(dpphen)]PF6 (1) and [Ir(ppz)2(tmphen)]PF6 (2) (ppz is 1-phenylpyrazole, dpphen is 4,7-diphenyl-1,10-phenanthroline and tmphen is 3,4,7,8-tetramethyl-1,10-phenanthroline) with phenanthroline based ancillary ligands were fabricated using air stable electrodes and their electroluminescent properties were investigated. LECs based on complex 1 emitted yellow electroluminescence (λmax 574 nm) with Commission Internationale de L’Eclairage (CIE) coordinates of (0.49, 0.50) while the complex 2 gave yellowish-green electroluminescence (λmax 537 nm) with CIE coordinates of (0.35, 0.58). The work done here reveals that the alkyl substituted phenanthroline ancillary ligand, tmphen shifts the light emission to the shorter wavelength region than the phenyl substituted dpphen ligand, resulting in the color tuning of the light-emitting devices. Density functional theory (DFT) calculations were performed to gain insight into the molecular surfaces of ___________________________________________________________________________ page 228 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS cationic iridium complexes and their electrochemical behaviors. Single layer LECs based on these complexes exhibited a high luminescence of 5199 and 4751 cd/m2 for complexes 1 and 2 respectively. The ionic liquid, 1-ethyl-3methylimidazolium hexafluorophosphate (EMIMPF6) was added to the light emitting layer and hence higher luminances were obtained than the pristine device. Ionic liquid modified zinc oxide injection layer for inverted organic lightemitting diodes Organic Electronics, 14, Issue 1, January 2013, 164-168 Hicham Brine, Juan F. Sánchez-Royo, Henk J. Bolink We have demonstrated a novel approach for fabricating efficient hybrid organic–inorganic light emitting diodes (HyLEDs) by introducing dopants into solutions processable metal oxides as an interfacial layer. The doped ZnO is prepared by adding ionic liquid (IL) to a precursor solution for the ZnO. In this way a heavily doped ZnO:ILs cathode was obtained that enhances the electron injection properties and assures a good wetting of the organic active materials. Atomic Force Microscopy as a Valuable Tool in an Innovative Multi-scale and Multi-technique Non-invasive Approach to Surface Cleaning Monitoring Procedia Chemistry, 8, 2013, 258-268 C. Pereira, I.M.P.L.V.O. Ferreira, L.C. Branco, I.C.A. Sandu, T. Busani To monitor and analyze the effectiveness of new cleaning formulations, using a combination of ionic liquids ([BMIM] [BF4] and [EMIM] [EtSO4]) and enzymes (three different proteases E.C.3.4.), we adopted a novel multi-scale non-invasive approach based with different instruments: the stereomicroscope (SM), the optical microscope (OM) with visible and fluorescence light, atomic force microscope (AFM) and scanning electron microscope (SEM). The combinations of these techniques allowed an extensive and complete characterization of the surface materials and were successfully applied for monitoring the cleaning process. Although the results showed in this work were obtained for this specific treatment, of removing proteinaceous varnish layer from documented reconstructions, it was demonstrated that the AFM monitoring protocol can be widely applied on everyday situations in the conservation science. Thermodynamic Behavior of FeCl3-H2O and HCl-FeCl3-H2O Systems – A Pitzer Model at 25 °C Procedia Earth and Planetary Science, 7, 2013, 14-18 L. André, C. Christov, A. Lassin, M. Azaroual ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 229 PUBLICATIONS Most of the speciation models of aqueous electrolyte systems are based on the “ion pairing and complexing approach”. They are only suitable for aqueous solutions with ionic strengths lower than about 1 eq.kgw-1. For highly saline solutions, an approach based on “specific-ion interactions” (the so-called “Pitzer approach”) provides much more accurate results. Various thermodynamic databases supporting the “Pitzer approach” exist, but they are often inconsistent and poorly documented. The number of chemical elements is limited because of the difficulties inherent to producing relevant experimental data for wide ranges of temperature, ionic strength, pH, and for low solubility metals and hydroxides, and also because of the difficulty in evaluation of consistent and accurate values for interaction parameters. This study presents a new set of parameters using the standard Pitzer formalism that is able to model the behavior of Fe-rich solutions and solid-liquid equilibria in binary FeCl3-H2O and mixed HCl-FeCl3-H2O systems at 25 °C. The new binary and mixing interaction parameters are adjusted in order to fit various independent experimental activity (water activity, osmotic coefficients) and ferric chloride salts solubility data. This work allows updating and improving thermodynamic databases for Fe(III) systems in order to simulate the complex geochemical behaviour of solutions and gas-brine-rock interactions in various applications in the geosciences or industrial processes. Nanoparticle Enhanced Ionic Liquids (NEILS) as Working Fluid for the Next Generation Solar Collector Procedia Engineering, 56, 2013, 631-636 Titan C. Paul, AKM. M. Morshed, Jamil A. Khan Next generation solar thermal collector requires working fluid with high heat storage capacity as well as high temperature thermal stability to reduce its operating cost. Ionic liquids (ILs) are considered as a potential working fluid for next generation solar collector due to suitable thermophysical properties. However, Nanoparticle Enhanced Ionic Liquids (NEILs), a class of nanofluids, can further enhance the thermophysical properties of ILs. In this study, an experimental assessment on NEILs was performed by measuring thermophysical property and evaluating forced convection performance. Experimental results show clear advantages of the NEILs over the base ILs both in heat storage capacity and heat transfer performance. Up to 6% enhancement in thermal conductivity, 23% enhancement in heat capacity, and 20% enhancement in convective heat transfer performance has been observed for the 1% (Weight%) aluminium oxide (Al2O3) enhanced ILs compared to the base ILs. Our current study lays the foundation for future studies to explore further investigation to evaluate NEILs as a potential working fluid for the next generation solar collectors. ___________________________________________________________________________ page 230 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Ionic Liquids: - The Novel Solvent for Removal of Dibenzothiophene from Liquid Fuel Procedia Engineering, 51, 2013, 314-317 Swapnil A. Dharaskar, Kailas L. Wasewar, Mahesh. N. Varma, Diwakar. Z. Shende, Chang Kyoo Yoo Ionic Liquids (ILs), a new class of green solvents, have recently been undergoing intensive research on the removal of thiophenic sulfur species (e.g., dibenzothiophene) from liquid fuels because of the limitations of the tradition hydrodesulfurization process in removing these species. In this work, deep extractive desulfurization of liquid fuels by different ionic liquids are studied and employed as promising extractants for the model liquid fuel containing dibenzothiophene (DBT). 1-butyl-3-methylimidazolium chloride [Bmim]Cl was the most promising and novel ionic liquid and performed the best among the studied ionic liquids under the same operating conditions. It can remove dibenzothiophene from the liquid fuel in the single stage extraction process with the maximum desulfurization efficiency 77.15% under mild reaction conditions. It was also found that [Bmim] Cl can be reused without regeneration with considerable extraction efficiency. Generalized PSRK Model for Prediction of Liquid Density of Ionic Liquids Procedia Engineering, 51, 2013, 386-394 N.K. Patel, M.H. Joshipura A simple and generalised expression for adjustable parameter for pure ionic liquids in conjunction with predictive-Soave- Redlich-Kwong (PSRK) approach is presented for prediction of pure IL density. The proposed expression is based on the correlation developed by Nasrifar and Moshfeghian for perfection of saturated liquid density for pure compounds. The generalized expression uses acentric factor and mass connectivity index of pure ionic liquids. A set of 47 pure ionic liquids with 735 data points and 4 different cohesion functions were used in the study. The results were compared with linear generalized model (LGM) developed by Valderrama to check appropriateness and accuracy of expression presented. It was found that the compound specific PSRK approach gives very accurate predictions and generalized expression is at par with LGM model. Further study would include use of other cohesion factor models. Deep Removal of Sulfur from Model Liquid Fuels using 1-Butyl-3Methylimidazolium Chloride Procedia Engineering, 51, 2013, 416-422 Swapnil A. Dharaskar, Kailas L. Wasewar, Mahesh. N. Varma, Diwakar. Z. Shende, Chang Kyoo Yoo ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 231 PUBLICATIONS Ionic liquids (ILs) as one kind of green solvents was studied and applied more and more with the development of green technology because of their unique physical and chemical properties. The removal of sulfur from liquid fuel using ionic liquids has been studied. The desulfurization efficiency of 1-butyl-3methylimidazolium chloride [Bmim]Cl has been tested. The effects of ionic liquid loading, extraction temperature and extraction time on the removal of dibenzothiophene from different model liquid fuels n-dodecane, n-octane, nhexane, and n-heptane were investigated. The highest extraction with 77.15% sulfur removal efficiency in a single stage extraction process was observed. Also the [Bmim]Cl can be reused in extraction without regeneration with considerable extraction effeicency. Nitroxide-mediated polymerization Review Article Progress in Polymer Science, 38, Issue 1, January 2013, 63-235 Julien Nicolas, Yohann Guillaneuf, Catherine Lefay, Denis Bertin, Didier Gigmes, Bernadette Charleux Nitroxide-mediated polymerization (NMP) is a controlled/living radical polymerization (CLRP) technique that enables the design of well-defined, functional and complex macromolecular architectures. This comprehensive review covers all aspects, features and achievements of NMP, from its discovery to 2012. All topics related to NMP are thoroughly discussed and detailed indepth: synthetic approaches to nitroxides and alkoxyamines, kinetic aspects and polymerization features, range of controllable monomers, polymer characterization, polymerization processes (ionic liquids, dispersed media, etc.), macromolecular coupling approaches, functionalization strategies, macromolecular architectures, bio-related and hybrid materials, industrial applications as well as environmental constraints. A new era for CSP? Renewable Energy Focus, 14, Issue 1, January–February 2013, 38-41 Gail Rajgor A new molten salt has been launched by Yara with the potential to drive down the costs of solar thermal energy and boost plant efficiency. Gail Rajgor spoke to the company's Emilio Iglesias to find out more. High-performance impedimetric genosensor based on biocompatible TiO2 nanoparticles supported carbon ionic liquid electrode Sensors and Actuators B: Chemical, 176, January 2013, 386-389 Wei Zhang ___________________________________________________________________________ page 232 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS A high-performance DNA hybridization biosensor was constructed with nanosized TiO2 supported carbon ionic liquid electrode (CILE) as the sensing interface. The morphology of TiO2 nanoparticles and electrochemical performance of the TiO2/CILE were systematically investigated. The decoration of CILE with nanosized TiO2 integrated the advantages of nanosized TiO2 and CILE, including large surface area, excellent conductivity, and fine biocompatibility, which provided a favorable platform for DNA detection. Remarkable change has been observed in the impedance spectra before and after hybridization of probe ssDNA with the target DNA under optimal conditions. The sequence-specific DNA of PML/RARA fusion gene from acute promyelocytic leukemia could be quantified in a wide range of 1.0 × 10−13 to 1.0 × 10−8 mol/L with a detection limit of 2.8 × 10−14 mol/L. The approach does not need oligonucleotide probe or target to be labeled previously, which makes it advantageous in terms of simplicity and noninvasiveness. Electrochemical determination of methyl parathion using a molecularly imprinted polymer–ionic liquid–graphene composite film coated electrode Sensors and Actuators B: Chemical, 176, January 2013, 818-824 Lijuan Zhao, Faqiong Zhao, Baizhao Zeng A molecularly imprinted polymer–ionic liquid–graphene composite film coated glassy carbon electrode (MIP–IL–EGN/GCE) was presented for the first time. It was fabricated by coating a GCE with IL-graphene oxide (GO) mixture, followed by MIP suspension. The resulting electrode was then conditioned at −1.3 V (vs SCE) in a Na2SO4 solution to make the GO turn to graphene (EGN). The MIP was prepared by free radical polymerization using methyl parathion (MP) as template, methacrylic acid as functional monomer, ethyleneglycol dimethacrylate as cross-linking reagent and 2,2′-azobis(isobutyronitrile) as initiator. The response property of MIP–IL–EGN/GCE to MP was studied. Under the optimized conditions, the peak current of MP was linear to its concentration in the range of 0.010–7.0 µM with a sensitivity of 12.5 µA/µM, and the detection limit was 6 nM (S/N = 3). When a 1.0 µM MP solution was determined for five times using a MIP–IL–EGN/GCE, the RSD of peak current was 2.3%; the electrode-to-electrode RSD was 6.4% (n = 5). The sensor also displayed high selectivity and stability. It was applied to the determination of MP in samples and the recovery was 97–110%. Amperometric glucose biosensor based on direct assembly of Prussian blue film with ionic liquid-chitosan matrix assisted enzyme immobilization Sensors and Actuators B: Chemical, 176, January 2013, 978-984 Yannan Zhang, Yu Liu, Zhenyu Chu, Lei Shi, Wanqin Jin ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 233 PUBLICATIONS A facile fabrication procedure was developed for the construction of glucose biosensor. Prussian blue (PB) was modified on the electrode through simple direct assembly process. The ionic liquid (IL) assisted chitosan (Chi) matrix was used for the glucose oxidase (GOx) immobilization on the PB electrode. Cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS) were used to evaluate the performance of the prepared GOx/Chi/IL/PB/Pt biosensor. The presence of IL (1-butyl-3-methylimidazolium tetrafluoroborate, [bmim]BF4) can effectively enhance the electron transfer rate and reduce the interfacial resistance. This biosensor exhibited a fast response time within 3 s, a linear range up from 0.01 to 4.2 mM, low detection limit of 5 µM and a sensitivity of 37.8 µA mM−1 cm−2. Because of the biocompatibility of the IL-Chi composite matrix, the biosensor exhibited satisfactory storage stability over 40 days with retention of 90.4% activity. Additionally, the biosensor exhibited good selectivity which was attributed to the low operating potential employed (−0.05 V vs. Ag/AgCl). Electrochemical and electromechanical properties of high-performance polymer actuators containing vapor grown carbon nanofiber and metal oxide Sensors and Actuators B: Chemical, 176, January 2013, 1065-1073 Naohiro Terasawa, Ichiroh Takeuchi The effects of metal oxide and an ionic liquid (IL) on the electrochemical and electromechanical properties of poly(vinylidene fluoride-cohexafluoropropylene) actuators were investigated using a vapor grown carbon nanofiber (VGCF)-IL gel electrode containing metal oxide, formed without using ultrasonication. The double-layer capacitance of the VGCF electrode containing MnO2 was larger than that of electrodes containing either only VGCF or RuO2/VGCF. A MnO2/VGCF electrode containing 1-ethyl-3methylimidazolium tetrafluoroborate (EMI[BF4]) gave the largest capacitance of those tested. The VGCF polymer actuator containing MnO2 surpassed the performance, in terms of strain and maximum generated stress, of actuators prepared with VGCF only, RuO2/VGCF, or single-wall carbon nanotubes (SWCNTs) only. The MnO2/VGCF actuator containing EMI bis(trifluoromethanesulfonyl)imide (EMI[TFSI]) gave the largest strain and the MnO2/VGCF actuator containing EMI[BF4] gave the largest maximum generated stress. The capacitance of the MnO2/VGCF/IL electrode and the strain for the MnO2/VGCF/IL actuator contribute to the pseudocapacitance. Both VGCF and MnO2 are necessary to produce actuators with large and rapid responses that surpass the performance of polymer actuators containing only VGCF, RuO2/VGCF, and only SWCNTs. Furthermore, the frequency dependence of the displacement response of the RuO2 or MnO2/VGCF polymer actuator was successfully simulated using an electrochemical kinetic model. The result for simulation of the electromechanical response of the RuO2 or ___________________________________________________________________________ page 234 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS MnO2/VGCF actuators provided the strain at a limit of low frequency and the time constant for the simulation. Comparison of electrochemical and electromechanical properties of a high performance carbon black polymer actuator and a single-walled carbon nanotube polymer actuator Sensors and Actuators B: Chemical, 176, January 2013, 1103-1109 Naohiro Terasawa, Kentaro Yamato The electrochemical and electromechanical properties of actuators prepared using a carbon black (CB)-ionic liquid (IL) gel electrode containing manganese oxide (MnO2) and formed without ultrasonication were compared with actuators prepared using only-CB, only-multi-walled carbon nanotubes (MWCNTs), onlyactivated multi-walled carbon nanotubes (MWCNT-COOH) and only-singlewalled carbon nanotubes (SWCNTs). The CB polymer actuator containing MnO2, prepared without ultrasonication, surpassed the strain performance of the only-CB, only-MWCNT, only-MWCNT-COOH and only-SWCNT actuators. The capacitance of the MnO2/CB/IL electrode contributes to the pseudocapacitance, and for low frequencies, the strain for the MnO2/CB/IL actuator is the dominant contributor to the pseudocapacitance. Therefore, it is considered that the mechanism for MnO2/CB/IL actuation is different from that for the only-SWCNT and only-MWCNT-COOH actuators. Both CB and MnO2 are required to produce a large strain actuator that surpasses the performance of the SWCNT polymer actuator and has characteristics sufficient for practical applications (e.g., in tactile displays). Assessing the natural resource use and the resource efficiency potential of the Desertec concept Solar Energy, 87, January 2013, 176-183 Tobias Samus, Bastian Lang, Holger Rohn Considering global warming, increasing commodity prices, and the dramatic consequences of the over-exploitation and overuse of resources, a transition to a renewable energy supply is necessary. This requires an (resource) efficient and renewable supply of operating reserve. In this article, a possible solution to this problem is analysed: the Desertec concept. It is meant to convert solar energy in areas with high solar irradiation into electrical energy by means of Concentrated Solar Power (CSP) transferring this energy by High Voltage Direct Current (HVDC) lines into the whole European Union Middle East and North Africa (EU-MENA) area. In order to assess the resource efficiency potential of Desertec, three different kinds of CSP plants (parabolic trough, Fresnel collector and central receiver of the building classes Inditep, Novatec and Solar Tres) including heat storage systems (Molten ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 235 PUBLICATIONS Salt and Phase-Changing-Material) and the necessary HVDC are analysed using the Material Input per Service Unit (MIPS) methodology. The assessment is accomplished for three different locations (Morocco, Tunisia and Egypt) and two points of time (2025 and 2050). With these results, a scenario of electricity supply in Germany in 2050 with a 20% share of solar power import is calculated. Central receivers are the most resource efficient ones: their consumption of abiotic materials is only half of parabolic trough plants and two thirds of Fresnel trough plants. Water and air consumption is the lowest of all analyzed CSP plants as well. The scenario for Germany’s fuel mix in 2050 shows that a predominantly renewable fuel mix reduces the consumption of abiotic materials by 75%, of water by 60% and of air by 45%. Only the consumption of biotic materials rises due to the higher share of biomass conversion.` Chapter 9 - Green Processes and High-Pressure Solvents Supercritical Fluid Science and Technology, 3, 2013, 215-238 Esteban Brignole, Selva Pereda In this chapter, the problem of sustainability of the chemical and pharmaceutical industries and the principles of green chemistry are outlined. In particular, the need for secure and environmentally safe solvents (ESSs) is pointed out. There are several ESS alternatives under study nowadays, like ionic liquids, polymeric solvents, and simple liquids like fatty esters; however, an increasing attention is being paid to supercritical fluids (SCFs) for a wide variety of applications in the chemical and pharmaceutical as well as in the materials and electronic industry. In the present chapter after an introduction to the fundamentals of SCF extraction, PEE principles are applied to several case studies of SCF—substrate mixtures of natural products with different types of phase behavior. Finally the application of SCF for supercritical micronization is reviewed and a case study is presented. High pressure phase behaviour of mixtures of hydrogen and the ionic liquid family [cnmim][Tf2N] The Journal of Supercritical Fluids, 73, January 2013, 126-129 S. Raeissi, A.M. Schilderman, C.J. Peters The high-pressure solubility of hydrogen gas in the ionic liquid 1-ethyl-3methylimidazolium bis(trifluoromethylsulphonyl)amide ([emim][Tf2N]) was measured experimentally in an equipment based on the synthetic technique. Measurements were carried out within a temperature range of 310–450 K and pressures up to 15 MPa. Hydrogen solubility was shown to be low in this ionic liquid, reaching a maximum concentration of about 6 mole percent at the highest ___________________________________________________________________________ page 236 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS temperatures and pressures investigated. Hydrogen solubility showed an “inverse” temperature effect, indicating increased solubility at higher temperatures in contrast to other commonly investigated gas solubilities in ionic liquids, such as carbon dioxide. Within the temperature and pressure range investigated, solubility isotherms on a pressure–concentration diagram approximated linear behaviour. It was also shown that the solubility of hydrogen increases as the alkyl side chain of the cation increases in size within the homologous family. Chapter 4 - Heterogeneous Catalysis for Biodiesel Production The Role of Catalysis for the Sustainable Production of Bio-fuels and Biochemicals, 2013, 93-136 Simona M. Coman, Vasile I. Parvulescu The chapter presents a critical analysis of the catalytic routes that have been investigated to date for the synthesis of biodiesel using esterification of fatty acids and transesterification of fatty acid esters. Organocatalysis using both acid and base catalysts, heterogeneous catalysis using inorganic acid and base catalysts, ionic resins, enzymes, and immobilized enzymes working in different solvents, including ionic liquids, have been suggested for providing efficient conditions to achieve high yields in this reaction. However, in many cases, the alcohol:acid or alcohol:oil ratios and temperatures were too high to afford an economic process. The stability of the catalysts represents another important feature analyzed in this chapter. Some of the systems leach, leading to active homogeneous species, or simply get deactivated. The conditions in which the reaction was activated (heating, microwave, or ultrasound) and the type of the reactors (batch, flow) were also found to be very important for the economy of this process. Production of Al–B master alloys by mixing KBF4 salt into molten aluminum Transactions of Nonferrous Metals Society of China, 23, Issue 1, January 2013, 294-300 Qing-liang WANG, Hong-sheng ZHAO, Zheng-guang LI, Li SHEN, Jiu-zhou ZHAO Two mixing techniques, the immersion method and the vortex method, were adopted in the production of Al–3%B master alloys since the generally used production route involving the direct addition of KBF4 salt to molten aluminum has several drawbacks. The experimental results demonstrate that the Al–B master alloys produced by the immersion method show a microstructure characterized by the appearances of AlB12 phase and many agglomerations of boride particles, while the Al–B master alloy produced by the vortex method ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 237 PUBLICATIONS exhibits a well dispersed microstructure of AlB2 particles in the matrix. The distinct microstructure features result from the differences in the stirring speed during the salt additions and the average size of the salt droplets achieved by the salt additions. Sonoluminescence quenching and cavitation bubble temperature measurements in an ionic liquid Ultrasonics Sonochemistry, 20, Issue 1, January 2013, 47-51 Parag M. Kanthale, Adam Brotchie, Franz Grieser, Muthupandian Ashokkumar A comparison between the temperatures within imploding acoustic cavitation bubbles and the extent of sonoluminescence (SL) quenching by C1–C5 aliphatic alcohols in 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO4], a well known imidazolium based room temperature ionic liquid (RTIL)), has been made at an ultrasound frequency of 213 kHz. The temperatures obtained ranged from 3500 ± 200 K, in neat [EMIM][EtSO4], to about 3200 ± 200 K in RTILalcohol containing solutions. It was also found that the SL intensity decreased with increasing concentration (up to 1 M) of the alcohols to a greater extent compared with the relative changes to the bubble temperatures. Both the extent of the reduction in the bubble temperatures and the SL quenching were much smaller than those obtained in comparable aqueous solutions containing aliphatic alcohols. Possible reasons for the differences in the observed trends between water/alcohol and [EMIM][EtSO4]/alcohol systems under sonication at 213 kHz are discussed. Aqueous ionic liquid based ultrasonic assisted extraction of four acetophenones from the Chinese medicinal plant Cynanchum bungei Decne Ultrasonics Sonochemistry, 20, Issue 1, January 2013, 180-186 Yinshi Sun, Zhengbo Liu, Jianhua Wang, Saifei Yang, Baiqing Li, Ning Xu In this study, an aqueous ionic liquid based ultrasonic assisted extraction (ILUAE) method for the extraction of the four acetophenones, namely 4hydroxyacetophenone (1), 2,5-dihydroxyacetophenone (2), baishouwubenzophenone (3) and 2,4-dihydroxyacetophenone (4) from the Chinese medicinal plant Cynanchum bungei was developed. Three kinds of aqueous l-alkyl-3-methylimidazolium ionic liquids with different anion and alkyl chain were investigated. The results indicated that ionic liquids (ILs) showed remarkable effects on the extraction efficiency of acetophenones. In addition, the ILUAE, including several ultrasonic parameters, such as the ILs concentration, solvent to solid ratio, power, particle size, temperature, and extraction time have been optimized. Under these optimal conditions (e.g., with 0.6 M [C4MIM]BF4, solvent to solid ratio of 35:1, power of 175 W, particle size of 60–80 mesh, temperature of 25 °C and time of 50 min), this approach gained the highest extraction yields of four acetophenones 286.15, 21.65, 632.58 and ___________________________________________________________________________ page 238 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS 205.38 µg/g, respectively. The proposed approach has been evaluated by comparison with the conventional heat-reflux extraction (HRE) and regular UAE. The results indicated that ILUAE is an alternative method for extracting acetophenones from C. bungei. Effect of non-ionic surfactants on transient cavitation in a megasonic field Ultrasonics Sonochemistry, 20, Issue 1, January 2013, 603-609 M. Keswani, S. Raghavan, P. Deymier High resolution chronoamperometry has been used to characterize the effect of two non-ionic surfactants, Triton® X-100 and NCW®-1002, on cavitation in aqueous solutions exposed to ∼1 MHz sound field. Specifically, using ferricyanide as the electroactive species, temporal variation of current during its reduction on a 25 µm Pt microelectrode has been measured and is used to elucidate transient cavity behavior. The chronoamperograms for solutions exposed to megasonic field show current ‘peaks’ riding on the baseline current. These current ‘peaks’ have been attributed to the diffusion of ferricyanide species concentrated at the liquid–vapor interface of a transient cavity at the end of its collapse. In the presence of surfactants, the frequency of occurrence of current ‘peaks’ with magnitude ⩾0.3 µA is found to increase indicating a higher number of transient cavity collapses. A simple mathematical model based on diffusion developed previously by the authors has been used to extract the maximum cavity size and range of distances between the center of the collapsing cavity and the electrode surface in the surfactant solutions. Removal of naphthenic acids from crude oil using amino acid ionic liquids Fuel, 108, 2013, 715-722 K. Anderson, P. Goodrich, C. Hardacre, A. Hussain, D.W. Rooney, D. Wassell A number of tetraalkylammonium and tetraalkylphosphonium amino acid based ionic liquids (AAILs) have been successfully used and recycled for the reactive extraction of naphthenic acids from crude oil and crude oil distillates. Spectral studies show that the mechanism by which this occurs is through the formation of a zwitterionic complex. Therein, the amino acid anion plays a key role in the formation of this complex. Improving high temperature heat capture for power generation in gasification plants International Journal of Heat and Mass Transfer, 61, 2013, 129-137 Barbara B. Botros, John G. Brisson As part of the gasification process, hot syngas is cooled to low temperatures for gas cleaning by generating high pressure steam in a radiant heat exchanger. The ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 239 PUBLICATIONS steam, in turn, is used to generate electric power. However, the very large temperature difference that exists between the syngas and generated high pressure steam results in significant losses during the heat transfer process. These losses can be reduced, and hence the overall plant efficiency improved, by choosing materials and working fluids that reduce the temperature difference in the syngas heat exchanger. A set of alternatives to high pressure steam is liquid metals or molten salts. These liquids can be kept at a pressure equal to the syngas pressure, reducing the tensile hoop stress in the heat exchanger tubes. Since the strength of steel decreases with temperature, reducing the hoop stress allows tubes (and the liquids inside them) to reach higher temperatures. The liquid metals or molten salt can then be used in a secondary heat transfer loop to transfer heat to a steam generator. This paper describes a cost-effective radiant heat exchanger that can be used to transfer heat from high temperature syngas to these alternative heat transfer fluids, and also quantifies the increase in overall IGCC plant efficiency by doing so. A capital cost assessment shows a small payback time and improved revenue is achieved by using this technology, making this a realistic option for gasification processes. Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities Journal of Environmental Chemical Engineering, 1, Issues 1–2, 2013, 18-22 Alex I. Wixtrom, Jessica E. Buhler, Charles E. Reece, Tarek M. Abdel-Fattah Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities. Ionic Liquids Assisted Synthesis of ZnO Nanostructures: Controlled Size, Morphology and Antibacterial Properties Journal of Materials Science & Technology, 29, Issue 6, 2013, 533-538 R. Rajiv Gandhi, S. Gowri, J. Suresh, M. Sundrarajan ___________________________________________________________________________ page 240 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Systematic analysis about the exploitation of imidazolium based ionic liquids (ILs), [BMIM] BF4 [IL1], [EMIM] BF4 [IL2] and [BMIM] PF6 [IL3] as the morphological template on the basic sol–gel method adopted synthesis of nanostructured zinc oxide (ZnO) is presented. X-ray diffraction (XRD), particle size analysis (PSA) and scanning electron microscopy (SEM) have been employed for the characterization of structure and morphology of the synthesized ZnO particles. Well-defined capsule like shaped morphology with lower nanosize is observed for the ZnO nanoparticles with IL1 than those with IL2 and IL3. This confirms that IL1 served as an effective templating material due to their unique properties. Especially the effective aggregation of ZnO particles with a self-organized frame of IL1 was the essential factor to produce the lower nanosized ZnO with capsule shaped structure. The synthesized ZnO samples with IL2 and IL3 fabricated the flake like shaped and rod like shaped morphologies in the range of nanoscale. The formed ZnO nanoparticles with IL2 exhibit higher nanosize than the ZnO nanoparticles produced by IL1, owing to shorter length of alkyl group in its cation which restricts steric effect and permits the nanoparticles to grow longer. Even though IL3 produced the discrete ZnO nanorods, the hydrophobic nature of IL3 created the higher nanosize than the ZnO nanoparticles formed by other two ionic liquids. Antibacterial properties of the synthesized ZnO nanostructures were investigated against Staphylococcus aureus (gram positive) and Escherichia coli (gram negative) bacteria by Agar diffusion test method. Microbial experiments indicate that the synthesized ZnO samples show a wide spectrum of antimicrobial activities and performed better against S. aureus than E. coli with the same concentration of ZnO. Room temperature ionic liquid/ZIF-8 mixed-matrix membranes for natural gas sweetening and post-combustion CO2 capture Journal of Membrane Science, 436, 2013, 221-231 Lin Hao, Pei Li, Tingxu Yang, Tai-Shung Chung We have investigated the effects of zeolite imidazolate framework-8 (ZIF-8) nanoparticles in miscible ionic liquid blend systems for natural gas sweetening and post-combustion CO2 capture. The miscible blend systems consists of a polymerizable room temperature ionic liquid (poly(RTIL)) and a “free” room temperature ionic liquids (RTILs). The poly(RTIL) is 1-vinyl-3-butyl imidazolium-bis (trifluoromethylsulfonyl) imidate ([vbim][NTf2]), while the RTIL is either (i) 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]), (ii) 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([emim][NTf2]) or (iii) 1-ethyl-3-methylimidazolium tetracyanoborate ([emim][B(CN)4]). Experimental results show that the free ionic liquids are miscible with poly(RTIL), while ZIF-8 are uniformly dispersed in the MMMs. The presence of ZIF-8 nanoparticles in the MMMs considerably improves gas permeability without much scarifying CO2/N2 and CO2/CH4 selectivities as compared to their poly(RTIL)/RTIL counterparts. The gas permeability of ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 241 PUBLICATIONS P[vbim][NTf2]/[emim][B(CN)4]/ZIF-8 comprising 25.8 wt% ZIF-8 exhibits a threefold increase in gas permeability. Both the semi-logarithmic addition and Maxwell equations are employed to analyze the transport mechanisms across the newly developed MMMs. The permeability vs. ZIF-8 content of P[vbim][NTf2]/ZIF-8, P[vbim][NTf2]/[emim][NTf2]/ZIF-8 follows exactly the Maxwell prediction, indicating these blend membranes are intrinsically heterogeneous with well dispersed ZIF-8 nanoparticles. However, an interesting phenomenon was observed in the P[vbim][NTf2]/[emim][B(CN)4]/ZIF-8 system where the homogeneous poly(RTIL)/RTIL phase turns into a more heterogeneous phase upon the adding of ZIF-8. As a result, a double employment of Maxwell equation is applied to analyze the enhanced gas permeability when a higher ZIF-8 loading is utilized. The P[vbim][NTf2]/[emim][B(CN)4]/ZIF-8 system with 25.8 wt% ZIF-8 exhibits impressive performance for post-combustion CO2/N2 (50/50 mol%) separation. It has a CO2 permeability of 906.4×3.348×10−19 kmol m/(m2 s pa) (906.4 barrer) and a CO2/N2 selectivity of 21 at 35 °C and 3.5 bar. Corrigendum to “New electrolyte membranes for Li-based cells: Methacrylic polymers encompassing pyrrolidinium-based ionic liquid by single step photo-polymerisation” [J. Membr. Sci. 423–424 (2012), 459–467] Journal of Membrane Science, 436, 2013, 232 C. Gerbaldi, Jijeesh R. Nair, S. Ferrari, A. Chiappone, G. Meligrana, S. Zanarini, P. Mustarelli, N. Penazzi, R. Bongiovanni No abstract is available for this article. Support effect on the catalytic activity and selectivity of SILP catalysts in isobutene trimerization Journal of Molecular Catalysis A: Chemical, 372, 2013, 51-57 Csaba Fehér, Eszter Kriván, József Kovács, Jenő Hancsók, Rita Skoda-Földes Oligomerization of isobutene has been carried out using silica supported Brønsted acidic ionic liquid catalysts. Silica supports with different particle size and textural properties have been used to prepare the catalysts. A close relationship between these properties and catalytic activity of the SILP material was observed. Silica supports with mesoporous structure could be converted to very active catalysts. On the other hand, the use of microporous supports resulted in the formation of catalysts with excellent C12 selectivity. Dioxygen oxidation of 1-phenylethanol with gold nanoparticles and Nhydroxyphthalimide in ionic liquid Journal of Molecular Catalysis A: Chemical, 372, 2013, 72-78 Hassan Hosseini-Monfared, Hajo Meyer, Christoph Janiak ___________________________________________________________________________ page 242 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Gold nanoparticles (Au-NPs) of 8 nm average diameter were obtained by thermal reduction under nitrogen from KAuCl4 in the presence of nbutylimidazol dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIm+BF4−). Characterization of the Au-NP was done by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Catalytic activities of the Au-NP/IL dispersion were evaluated in the oxidation of 1-phenylethanol at 100 and 160 °C under 4 bar pressure of dioxygen in a base-free system. Au-NP in combination with the radical initiator Nhydroxyphthalimide (NHPI) showed good conversion and selectivity for the oxidation of 1-phenylethanol to acetophenone through formation of an αhydroxy carbon radical. The concomitant side products di(1-phenylethyl)ether and di(1-phenylethyl)peroxide were rationalized by an equilibrium due to the IL matrix of the α-hydroxy carbon radical with the 1-phenylethoxy radical. Maximum turnover number was ∼5200 based on the total number of moles of gold but a factor of about six larger, TON ≈ 31 300, when only considering the Au-NP surface atoms. The fraction (NS/NT) of exposed surface atoms (NS ≈ 2560) for an average 8 nm Au-NP (having NT ≈ 15 800 atoms in a ∼17shell icosahedral or cuboctahedral particle) was estimated here as 0.16. Silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepinium chloride (SB-DBU)Cl as a highly efficient, heterogeneous and recyclable silicasupported ionic liquid catalyst for the synthesis of benzo[b]pyran, bis(benzo[b]pyran) and spiro-pyran derivatives Journal of Molecular Catalysis A: Chemical, 372, 2013, 137-150 Alireza Hasaninejad, Nooshin Golzar, Maryam Beyrati, Abdolkarim Zare, Mohammad Mahdi Doroodmand The reaction of 3-chloropropyl silica (SilprCl) with 1,8diazabicyclo[5.4.0]undec-7-ene (DBU) in dry acetone affords silica-bonded 5-npropyl-octahydro-pyrimido[1,2-a]azepinium chloride (SB-DBU)Cl as a new silica-supported ionic liquid catalyst. Afterward, (SB-DBU)Cl is used for the efficient synthesis of 4H-benzo[b]pyran derivatives via the one-pot, threecomponent reaction of carbonyl compounds (cyclohexane-1,3-dione, 5,5dimethylcyclohexane-1,3-dione or 3-methyl-1-phenyl-2-pyrazolin-5-one) with aromatic aldehydes and alkylmalonates. Moreover, some novel bis(benzo[b]pyran)s and a broad range of structurally diverse spiro-pyrans containing oxindole and/or quinoxaline moiety in their structures are synthesized using (SB-DBU)Cl. The catalyst is recycled and reused fifteen times with unchanged yield. Enzymatic synthesis of 6- and 6′-O-linoleyl-α-D-maltose: From solvent-free to binary ionic liquid reaction media ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 243 PUBLICATIONS Journal of Molecular Catalysis B: Enzymatic, 90, 2013, 98-106 Fabian Fischer, Manuel Happe, Jessica Emery, Antoine Fornage, Rolf Schütz The eco-efficient lipase catalyzed synthesis of sugar fatty acid ester surfactants from renewable commodities is a stimulating challenge in biotransformation. The biocatalytic investigations went from solvent-free and minimal ionic liquid use to bulk organic solvents, and binary solvents thereof. Disaccharide maltose was acylated with linoleic acid (C18:2) on the primary O-6,6′ hydroxyl functions. The ionic liquid [emim][MeSO3] and the potentially renewable acetone enabled best conversions. Binary solvents like acetone/DMF and [emim][MeSO3]/[bmpyr][PF6] tended to double conversions. The lipase selection is also crucial and the enzymes Pseudomonas cepacia and immobilized Candida antarctica allowed highest yields in a screening with 10 different lipases. Also other non-solvent parameters such as reaction time and molecular sieve content improved maltose transformation further up to 82%. Analysis by HPLC, ESI-MS, and NMR indicated the formation of mono-6 or 6′-O-linoleylα-d-maltose as a mixture of two regioisomers in a 1.4:1 ratio. From an applied point of view, the best solvent is acetone. Unlike ionic liquids and binary mixtures, it is easily removable from reaction mixtures. Moreover, acetone is to some degree a green solvent as it can be produced directly from renewable feedstock. Effect of ionic liquids, organic solvents and supercritical CO2 pretreatment on the conformation and catalytic properties of Candida rugosa lipase Journal of Molecular Catalysis B: Enzymatic, 90, 2013, 123-127 Yun Liu, Dawei Chen, Yunjun Yan The objective of this work is to assess the structure and activity of Candida rugosa lipase (CRL) pretreated with seventeen ionic liquids (ILs), five organic solvents and super-critical carbon dioxide (SC-CO2). The results revealed that anion selection of ILs showed generally much greater effects on CRL esterification activity than cation choice, and CRL pretreated by ILs with strong water miscible properties showed very low esterification activity. The highest CRL activity treated with ILs [Hmim][PF6] was obtained with the value of 45078.0 U/g-protein. Furthermore, the CRL activities pretreated with five conventional organic solvents were also examined and the values increased with the log P decrease of organic solvents when log P was lower than 2.0. Finally, the CRL activities were respectively 1.2- and 1.3-fold higher over the untreated ones after pretreatment with sub- and super-critical CO2 under the pressures of 6 MPa and 15 MPa at 40 °C for 20 min. Further analyses via FT-IR demonstrated that the high activity of CRL pretreated with ILs, organic solvents and SC-CO2 was probably caused by the changes of CRL secondary structure. In conclusion, the results in this work will be helpful for us to choose the suitable reaction medium in CRL biocatalysis and biotransformation reactions. ___________________________________________________________________________ page 244 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Purification of used eutectic (LiCl–KCl) salt electrolyte from pyroprocessing Journal of Nuclear Materials, 437, Issues 1–3, 2013, 47-54 Yung-Zun Cho, Tae-Kyo Lee, Hee-Chul Eun, Jung-Hoon Choi, In-Tae Kim, Geun-Il Park The separation characteristics of surrogate rare-earth fission products in a eutectic (LiCl–KCl) molten salt were investigated. This system is based on the eutectic salt used for the pyroprocessing treatment of used nuclear fuel (UNF). The investigation was performed using an integrated rare-earth separation apparatus comprising a precipitation reactor, a solid detachment device, and a layer separation device. To separate rare-earth fission products, a phosphate precipitation method using both Li3PO4 and K3PO4 as a precipitant was performed. The use of an equivalent phosphate precipitant composed of 0.408 molar ratio-K3PO4 and 0.592 molar ratio-Li3PO4 can preserve the original eutectic ratio, LiCl-0.592 molar ratio (or 45.2 wt%), as well as provide a high separation efficiency of over 99.5% under conditions of 550 °C and Ar sparging when using La, Nd, Ce, and Pr chlorides. The mixture of La, Nd, Ce, and Pr phosphate had a typical monoclinic (or monazite) structure, which has been proposed as a reliable host matrix for the permanent disposal of a high-level waste form. To maximize the reusability of purified eutectic waste salt after rare-earth separation, the successive rare-earth separation process, which uses both phosphate precipitation and an oxygen sparging method, were introduced and tested with eight rare-earth (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) chlorides. In the successive rare-earth separation process, the phosphate reaction was terminated within 1 h at 550 °C, and a 4–8 h oxygen sparging time were required to obtain over a 99% separation efficiency at 700–750 °C. The mixture of rare-earth precipitates separated by the successive rare-earth separation process was found to be phosphate, oxychloride, and oxide. Through the successive rare-earth separation process, the eutectic ratio of purified salt maintained its original value, and impurity content including the residual precipitant of purified salt can be minimized. Effect of the UO2 form on the electrochemical reduction rate in a LiCl–Li2O molten salt Journal of Nuclear Materials, 437, Issues 1–3, 2013, 178-187 Eun-Young Choi, Jong-Kook Kim, Hun-Suk Im, In-Kyu Choi, Sang-Ho Na, Jae Won Lee, Sang Mun Jeong, Jin-Mok Hur Electrochemical reductions of various UO2 forms were investigated in a molten LiCl–Li2O electrolyte. The study focused on the influence of their sizes and densities on the reduction rate by running experiments with eight UO2 forms. They can be classified into porous and dense forms. The porous forms are one ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 245 PUBLICATIONS granule and four porous pellets with different densities (55%, 60%, 70% and 80%), all of which were fabricated in our laboratory. The dense forms were prepared by crushing dense pellets, and these were similar in size to the porous pellets and the granules. Systematic comparisons of the reduction rate among the tested UO2 forms revealed that a lower density and smaller size of UO2 led to a faster reduction rate. Particularly, attention was focused on the observation that the size of the UO2 provides more dominant effect on the reduction rate than the density. Effect of moisture on corrosion of Ni-based alloys in molten alkali fluoride FLiNaK salt environments Journal of Nuclear Materials, 437, Issues 1–3, 2013, 201-207 Fan-Yi Ouyang, Chi-Hung Chang, Bo-Chien You, Tsung-Kuang Yeh, Ji-Jung Kai We investigated the corrosion characteristics on several selected alloys at 600 and 700 °C in FLiNaK molten salts with different moisture contents. HastelloysN and Hastelloys-B3 exhibited better corrosion resistances, while Haynes 263 showed the poorest corrosion resistance. The mass loss of the tested alloys is primarily determined by the purity of FLiNaK salts; however, the effect of temperature becomes more important on the mass loss of the tested alloys in the non-purified FLiNaK salts. When the residual moisture is present in the FLiNaK salts, the mass losses of the tested alloys varied linearly with original Cr content plus one-third of Mo content. The results of structural characterization revealed that the tested alloys in the FLiNaK salts with higher moisture content would aggravate intergranular corrosion and pitting. Synthesis of flower-like Boehmite (γ-AlOOH) via a one-step ionic liquidassisted hydrothermal route Journal of Solid State Chemistry, 202, 2013, 305-314 Zhe Tang, Jilei Liang, Xuehui Li, Jingfeng Li, Hailing Guo, Yunqi Liu, Chenguang Liu A simple and novel synthesis process, one-step ionic liquid-assisted hydrothermal synthesis route, has been developed in the work to synthesize Bohemithe (γ-AlOOH) with flower-like structure. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscope (SEM). Ionic liquid [Omim]+Cl−, as a template, plays an important role in the morphology and pore structure of the products due to its strong interactions with reaction particles. With the increase in the dosage of ionic liquid [Omim]+Cl−, the morphology of the γ-AlOOH was changed from initial bundles of nanosheets (without ionic liquid) into final well-developed monodispersed 3D flower-like architectures ___________________________________________________________________________ page 246 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS ([Omim]+Cl−=72 mmol). The pore structure was also altered gradually from initial disordered slit-like pore into final relatively ordered ink-bottle pore. Furthermore, the proposed formation mechanism and other influencing factors such as reaction temperature and urea on formation and morphology of the γAlOOH have also been investigated. Three dimensional BiOX (X=Cl, Br and I) hierarchical architectures: facile ionic liquid-assisted solvothermal synthesis and photocatalysis towards organic dye degradation Materials Letters, 100, 2013, 285-288 Xiaoyan Qin, Hefeng Cheng, Wenjun Wang, Baibiao Huang, Xiaoyang Zhang, Ying Dai High-crystalline hierarchical BiOX (X=Cl, Br and I) microspheres were prepared by a generalized ionic liquid-assisted solvothermal method. The asprepared BiOX (X=Cl, Br and I) microspheres were uniform in size and the average diameters ranged from one to several micrometers, which were assembled by numerous interlaced nanosheets. According to the UV–Vis diffuse reflectance spectra, the band gaps were calculated to be 3.20, 2.72 and 1.76 eV for the BiOCl, BiOBr and BiOI samples, respectively. Evaluated by the decomposition of methyl orange (MO) solution, the BiOI product exhibited much better photocatalytic efficiency to BiOCl and BiOBr samples, which could respond to more visible light as well as facilitate the spatial transfer of the photoexcited carriers. Manipulating the morphology and textural property of γ-AlOOH by modulating the alkyl chain length of cation in ionic liquid Materials Research Bulletin, 48, Issue 6, 2013, 2351-2360 Zhe Tang, Xiaofu Hu, Jilei Liang, Jinchong Zhao, Yunqi Liu, Chenguang Liu We demonstrated that the morphology and textural property of γ-AlOOH can be tuned by modulating the alkyl chain length of cation in [Cnmim]+Cl− (n = 4, 8, 16). Using the short alkyl chain length-based [C4mim]+Cl− as the structuredirected reagent, the morphology of γ-AlOOH was not changed and preserved as the hollow sphere structure in all experiments. The specific area and the number of small meso-pores of γ-AlOOH increased with the increase of [C4mim]+Cl− dosage. While, using the larger alkyl chain length-based ionic liquids as the softtemplate, such as [C8mim]+Cl− and [C16mim]+Cl−, the morphologies of γAlOOH were changed from initiative hollow spheres into the final microflowers. The specific areas of γ-AlOOH firstly increased then decreased with the increase of their dosage. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and Transmission Electron Microscopy (TEM). ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 247 PUBLICATIONS Furthermore, the possible formation mechanisms of γ-AlOOH have been proposed. Synthesis and luminescent properties of nonaggregated YAG:Ce3+ phosphors via the molten salt synthesis method Materials Science in Semiconductor Processing, 16, Issue 3, 2013, 679-685 Chuanlei Wu, An Luo, Guoping Du, Xiaomei Qin, Wangzhou Shi In this work, we synthesized nonaggregated YAG:Ce3+ phosphor powders using the molten salt synthesis method. The effects of synthesis temperature and time on the crystallization process, microstructures, and luminescent properties of the YAG:Ce3+ phosphors were studied. The results indicate that pure YAG:Ce3+ phosphors can be obtained at about 400 °C using NaNO2–KNO2 as the molten flux. Optimal synthesis conditions and Ce3+ doping concentration for the best luminescent properties for YAG:Ce3+ phosphors were determined. Fabrication of single crystal field-effect transistors with phenacene-type molecules and their excellent transistor characteristics Organic Electronics, 14, Issue 6, 2013, 1673-1682 Xuexia He, Ritsuko Eguchi, Hidenori Goto, Eri Uesugi, Shino Hamao, Yasuhiro Takabayashi, Yoshihiro Kubozono Single crystal field-effect transistors (FETs) using [6]phenacene and [7]phenacene show p-channel FET characteristics. Field-effect mobilities, µs, as high as 5.6 × 10−1 cm2 V−1 s−1 in a [6]phenacene single crystal FET with an SiO2 gate dielectric and 2.3 cm2 V−1 s−1 in a [7]phenacene single crystal FET were recorded. In these FETs, 7,7,8,8-tetracyanoquinodimethane (TCNQ) was inserted between the Au source/drain electrodes and the single crystal to reduce hole-injection barrier heights. The µ reached 3.2 cm2 V−1 s−1 in the [7]phenacene single crystal FET with a Ta2O5 gate dielectric, and a low absolute threshold voltage |VTH| (6.3 V) was observed. Insertion of 2,3,5,6-tetrafluoro-7,7,8,8tetracyanoquinodimethane (F4TCNQ) in the interface produced very a high µ value (4.7–6.7 cm2 V−1 s−1) in the [7]phenacene single crystal FET, indicating that F4TCNQ was better for interface modification than TCNQ. A single crystal electric double-layer FET provided µ as high as 3.8 × 10−1 cm2 V−1 s−1 and |VTH| as low as 2.3 V. These results indicate that [6]phenacene and [7]phenacene are promising materials for future practical FET devices, and in addition we suggest that such devices might also provide a research tool to investigate a material’s potential as a superconductor and a possible new way to produce the superconducting state. Fabrication of gas sensor based on p-type ZnO nanoparticles and n-type ZnO nanowires Sensors and Actuators B: Chemical, 182, 2013, 190-196 ___________________________________________________________________________ page 248 MOLTEN SALTS & IONIC LIQUIDS N°108 PUBLICATIONS Cheng-Liang Hsu, Kuan-Chao Chen, Tsung-Ying Tsai, Ting-Jen Hsueh This investigation studies the feasibility of synthesizing high-density transparent p-type ZnO nanoparticles and n-type ZnO nanowires on a glass substrate at 650 °C using the self-catalyzed vapor–liquid–solid method. The doping impurity is Sb, which reduces the concentration of electrons in n-type nanowires and increases the concentration of holes in p-type nanoparticles. XRD spectra clearly include a strong peak that is associated with the wurtzite structure and very weak peaks that are associated with Sb2O3. All XRD peaks of the ZnO sample shift by a small angle upon doping by Sb. The Hall effect indicates that ZnO nanowires and ZnO:Sb nanoparticles are n-type and p-type, respectively. The Sb atoms produce the Moiré pattern and cause stacked faults to form nanoparticles as determined by HRTEM. The reaction between ethanol and ionic oxygen species yield electrons, which increase the conductivity of the n-type nanowires and reduce the conductivity of the p-type nanoparticles. The responses of p-type ZnO nanoparticles/n-type ZnO nanowires to gas are dominated by those of ptype sensors at 25 °C and n-type sensors above 200 °C. New materials in solid-phase microextraction TrAC Trends in Analytical Chemistry, 47, 2013, 68-83 Jianqiao Xu, Juan Zheng, Jingyu Tian, Fang Zhu, Feng Zeng, Chengyong Su, Gangfeng Ouyang We review the new and most commonly used coating materials for solid-phase microextraction (SPME) in the past five years. We discuss ionic liquids (ILs), polymeric ILs, graphene, carbon nanotubes, molecularly imprinted polymers and metal-organic frameworks, based on the recent trends in SPME-fiber coatings. The designable basic structures indicate the possibilities for developing more task-specific SPME fibers using these materials. High-energy EXAFS study of molten GdCl3 systems Journal of Molecular Liquids 187 (2013) 94–98 Y. Okamoto, H. Shiwaku, T. Yaita, S. Suzuki, M. Gaune-Escard The local structure of molten GdCl3 and its mixture in LiCl–KCl eutectic was investigated by Gd K-edge extended X-ray absorption fine structure (EXAFS) technique. As the result of curve fitting analysis, the nearest Gd3+–Cl− distance was 2.74 ± 0.02 Å with coordination number 6.5 ± 0.3 in the pure melt. On the other hand, those in the 10% GdCl3 mixture melt decreased to 2.70 ± 0.01 Å and 6.1 ± 0.3, respectively. These results suggest that octahedral coordination (GdCl6)3− structure is formed and stabilized by mixing with the alkali chlorides. The result was compared with ___________________________________________________________________________ MOLTEN SALTS & IONIC LIQUIDS N°108 page 249 PUBLICATIONS that of YCl3 and LaCl3 in LiCl–KCl eutectic melt. ___________________________________________________________________________ page 250 MOLTEN SALTS & IONIC LIQUIDS N°108