Paolo Pescarmona
University of Groningen, Chemical Engineering, Faculty Member
- I am currently Associate Professor in Sustainable Chemical Products and Catalysis at the University of Groningen, the... moreI am currently Associate Professor in Sustainable Chemical Products and Catalysis at the University of Groningen, the Netherlands (since November 2017). The position encompasses research and teaching tasks, the management of the acquired funding and the supervision of post-doc, Ph.D. and Master projects. My research approach involves the rational design and development of catalytic materials for applications of academic and industrial relevance, with a special focus on green chemistry. All aspects of the development of catalysts (heterogeneous and homogeneous) are covered: from the synthesis to the characterisation and testing. The targeted applications include CO2 fixation, biomass conversion, catalytic oxidations, photocatalysis, electrocatalysis and the use of high-throughput techniques for the synthesis and testing of catalysts in liquid phase and in supercritical CO2.edit
Due to their high volumetric and gravimetric capacities, Li-ion batteries (LiBs) are currently considered as the only viable energy storage solution for portable electronics and hybrid vehicles. Nevertheless, concerns on the availability... more
Due to their high volumetric and gravimetric capacities, Li-ion batteries (LiBs) are currently considered as the only viable energy storage solution for portable electronics and hybrid vehicles. Nevertheless, concerns on the availability of Li resources and their uneven distribution across the world are growing. As an alternative, Na-ion batteries (NiBs) are highly attractive due to the abundance of Na as well as its electrochemical similarity with Li. Na is also environmentally benign, thus promising a more sustainable energy storage. Although NiBs are unlikely to outperform LiBs in energy density, they are being actively pursued for low-cost grid storage where size or weight is not the most critical factor. The identification of a high-performance anode is a key challenge, particularly for NiBs. Anode materials investigated so far for NiBs can be classified into three categories: (i) layered materials, such as titania or titanates and transition metal dichalcogenides with a specif...
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In this work, we present a comprehensive study on the electrocatalytic reduction of fructose to sorbitol and mannitol, in mild alkaline medium (pH = 11.3), and by using a Cu-wire...
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Hereby, I would like to propose to investigate an aspect of the spread of the COVID-19 virus through surfaces that, to the best of my knowledge, has not been considered in detail: the use of cash in daily transactions. The question is:... more
Hereby, I would like to propose to investigate an aspect of the spread of the COVID-19 virus through surfaces that, to the best of my knowledge, has not been considered in detail: the use of cash in daily transactions. The question is: would the use of contactless transactions help in limiting the spread of the COVID-19 virus?
A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like... more
A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Brønsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Brønsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Brønsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Brønsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Brønsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent.
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Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types... more
Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely
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A new, two-step nanocasting method was developed to prepare N-doped ordered mesoporous carbon (NOMC) electrocatalysts for the reduction of O2 to H2O2. Our strategy involves the sequential pyrolysis of two inexpensive and readily available... more
A new, two-step nanocasting method was developed to prepare N-doped ordered mesoporous carbon (NOMC) electrocatalysts for the reduction of O2 to H2O2. Our strategy involves the sequential pyrolysis of two inexpensive and readily available N and C precursors, i.e. aniline and dihydroxynaphthalene (DHN), inside the pores of a SBA-15 hard silica template to obtain N-doped graphitic carbon materials with wellordered pores and high surface areas (764 and 877 m2g−1). By tuning the ratio of carbon sources to silica template, it was possible to achieve an optimal filling of the pores of the SBA-15 silica and to minimise -doped ordered mesoporous carbon
Bimetallic zeolite Beta in bead format and containing Al sites with Brønsted acid behavior and Sn, Zr or Hf sites with Lewis acid character, were prepared using a two-step synthetic route. First, zeolite Beta in the format of macroscopic... more
Bimetallic zeolite Beta in bead format and containing Al sites with Brønsted acid behavior and Sn, Zr or Hf sites with Lewis acid character, were prepared using a two-step synthetic route. First, zeolite Beta in the format of macroscopic beads (400 to 840 μm) with hierarchical porosity (micropores accessed through meso- and macropores in the range of 30 to 150 nm) were synthesized by hydrothermal crystallization in the presence of anion-exchange resin beads as hard template and further converted into their H-form. Next, the zeolite beads were partially dealuminated using different concentrations of HNO3 (i.e., 1.8 or 7.2 M), followed by grafting with one of the above-mentioned metals (Sn, Zr or Hf) to introduce Lewis acid sites. These bimetallic zeolites were tested as heterogeneous catalysts in the conversion of dihydroxyacetone (DHA) to methyl lactate (ML). The Sn-containing zeolite Beta beads treated by 1.8 M HNO3 and grafted with 27 mmol of SnCl4 (Sn-deAl-1.8-Beta-B) demonstrate...
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We report a novel and upscalable method to synthesise small, highly dispersed Bi nanoparticles on activated carbon. This electrocatalyst displays outstanding selectivity (FE > 99% at −1.07 V vs. RHE) and stability in the conversion of... more
We report a novel and upscalable method to synthesise small, highly dispersed Bi nanoparticles on activated carbon. This electrocatalyst displays outstanding selectivity (FE > 99% at −1.07 V vs. RHE) and stability in the conversion of CO2 to formate.
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Pickering-stabilized antibubbles were used as a new method to encapsulate Lactobacillus casei. Antibubbles consist of one or more liquid droplets within a shell of gas. The antibubbles were prepared from a water-in-oil-in-water (W/O/W)... more
Pickering-stabilized antibubbles were used as a new method to encapsulate Lactobacillus casei. Antibubbles consist of one or more liquid droplets within a shell of gas. The antibubbles were prepared from a water-in-oil-in-water (W/O/W) emulsion stabilized by silica particles, which was then freeze-dried to remove the water and oil phases, before being subsequently reconstituted in water. Different oil phases and aqueous phase compositions were tested for their effect on the survival of the bacteria. The survival of L. casei after encapsulation using decane was 29.8 ± 2.1% in antibubbles containing 10% (w/v) maltodextrin plus 8% (w/v) sucrose, which is comparable to the survival when bacteria were freeze-dried without being encapsulated. Encapsulation within antibubbles led to a 10 to 30 times higher survival of L. casei at pH 2 in comparison with unencapsulated bacteria. This study shows that probiotics can be encapsulated within a shell of gas through the use of antibubbles and tha...
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High-surface area Nb2O5 nanoparticles were synthesised by a novel supercritical-CO2-assisted method (Nb2O5-scCO2) and were applied for the first time as a heterogeneous catalyst in the oxidative coupling of aniline to...
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Multifunctional catalytic systems consisting of physical mixtures of (i) bimetallic Au-Pd nanoparticles (average size of 3-5 nm) supported on functionalised carbon nanotubes (CNTs) and (ii) Sn-MCM-41 nanoparticles (50-120 nm), were...
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The role of water as highly effective hydrogen bond donor (HBD) for promoting the coupling reaction of CO2 with a variety of epoxides was demonstrated under very mild conditions (25 °C ≤ T ≤ 60 °C, 2 bar ≤ p(CO2) ≤ 10 bar). Water led to a... more
The role of water as highly effective hydrogen bond donor (HBD) for promoting the coupling reaction of CO2 with a variety of epoxides was demonstrated under very mild conditions (25 °C ≤ T ≤ 60 °C, 2 bar ≤ p(CO2) ≤ 10 bar). Water led to a dramatic increase in the cyclic carbonate yield when employed in combination with Bu4NI, while it had a detrimental effect with the corresponding bromide and chloride salts. The efficiency of water in promoting the activity of the organic halide was compared with state-of-the-art HBDs. Although water requires higher molar loadings to achieve similar degree of conversion of CO2 and styrene oxide into the corresponding cyclic carbonate under the same, mild reaction conditions, its environmental friendliness and much lower cost make it a very attractive alternative as HBD. The effect of different parameters such as the amount of water, CO2 pressure, reaction temperature, and nature of the organic halide used as catalyst was investigated using a high-throughput reactor unit. The highest catalytic activity was achieved with either Bu4NI or PPNI: with both systems, the cyclic carbonate yield at 45 °C with different epoxide substrates could be increased by a factor two or more by adding water as a promoter, while retaining high selectivity. Water is an effective hydrogen bond donor even at room temperature, allowing to reach 85% conversion of propylene oxide with full selectivity towards propylene carbonate in combination with Bu4NI (3 mol%).
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The reaction between carbon dioxide and epoxides is an attractive pathway for CO2-utilisation as it leads to the formation of two different, yet both valuable products: cyclic and polymeric carbonates....
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A green electrochemical alternative: doped ordered mesoporous carbons are active and selective electrocatalysts for the reduction of nitrobenzene to aniline.
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This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via... more
This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via Diels-Alder (DA) cycloaddition. Notably, the incorporation of 5 wt.% of MWCNTs results in an increased modulus of the material, and makes it thermally and electrically conductive. Analysis by X-ray photoelectron spectroscopy indicates that MWCNTs, due to their diene/dienophile character, covalently interact with the matrix via DA reaction, leading to effective interfacial adhesion between the components. Raman spectroscopy points to a more effective graphitic ordering of MWCNTs after reaction with PK-Fu and B-Ma. After crosslinking the obtained composite via the DA reaction, the softening point (tan(δ) in dynamic mechanical analysis measurements) increases up to 155 °C, as compared to the value of 130 °C for the PK-Fu crosslinked with B-Ma and that of...
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Metal-organic frameworks with accessible Lewis acid sites are finding increasing application in the field of heterogeneous catalysis. However, the structural instability of MOFs when they are exposed to high temperature or high pressure... more
Metal-organic frameworks with accessible Lewis acid sites are finding increasing application in the field of heterogeneous catalysis. However, the structural instability of MOFs when they are exposed to high temperature or high pressure often limits their applicability. In this study, two strategies were applied to achieve a MOF catalyst with high stability, activity and selectivity in the reaction of CO2 with styrene oxide to produce styrene carbonate. In the first approach, a MOF with linkers with high connectivity as MIL-100(Cr) was studied, leading to promising activity and recyclability in consecutive catalytic runs without loss of activity. In the second strategy, a MOF with linkers with lower connectivity but with encapsulated Keggin phosphotungstic acid was prepared. However, the activity of this catalyst decreased upon reuse as a consequence of deterioration of the metal-organic framework. Further investigations were dedicated to the enhancement of the catalytic performance of MIL-100 and included the variation of the metal centre as well as the type and loading of organic salts acting as nucleophile source. This allowed tuning the nature of the organic halide to the specific porous structure of MIL-100(Cr) in order to prevent diffusion limitations. The best catalytic performance was obtained with MIL-100(Cr) in combination with EMIMBr, which achieved very high styrene carbonate yield (94%) with complete selectivity after 18h of reaction at mild temperature (60°C).
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Iron-containing N-doped carbon materials are active electrocatalysts for the cogeneration of hydroxylamine and electricity in a H2–NO fuel cell, which is a promising alternative to the present industrial synthesis.
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Three-dimensional mesoporous silicates of the TUD-1 family were synthesised with different metals (Zr, Hf and Sn) incorporated in the framework of the material. The mesoporosity of the prepared TUD-1s was confirmed by X-ray diffraction... more
Three-dimensional mesoporous silicates of the TUD-1 family were synthesised with different metals (Zr, Hf and Sn) incorporated in the framework of the material. The mesoporosity of the prepared TUD-1s was confirmed by X-ray diffraction (XRD), nitrogen physisorption and TEM. The incorporation of the metals in the silicate structure was investigated by FT-IR and UV–Vis spectroscopy. All three TUD-1 materials present a combination of Lewis and mild Bronsted acid sites, as determined by TPD-FT-IR of pyridine adsorption. The metal-containing TUD-1 materials were tested as solid acid catalysts for the conversion of three bio-based compounds into valuable chemical products. In the conversion of dihydroxyacetone into ethyl lactate, complete selectivity towards the desired lactate product was achieved with Zr-, Hf- and Sn-TUD-1. The three heterogeneous catalysts displayed similar activity, with Hf-TUD-1 reaching the highest conversion and metal-based turnover number. Sn-TUD-1 also displayed high activity and selectivity in two acetalisation reactions, i.e. the synthesis of solketal from acetone and glycerol and the reaction of vanillin with propylene glycol. The catalytic performance of these TUD-1 materials is ascribed to the high accessibility of their active sites and to the suitable combination of acid sites. The catalysts were successfully reused in consecutive runs and did not suffer from leaching.
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Polycarbonates can be prepared by the copolymerization of epoxides with carbon dioxide as an inexpensive, abundant, nontoxic, and renewable feedstock. This review covers the synthesis, the physicochemical properties, and the growing... more
Polycarbonates can be prepared by the copolymerization of epoxides with carbon dioxide as an inexpensive, abundant, nontoxic, and renewable feedstock. This review covers the synthesis, the physicochemical properties, and the growing applications of this class of green polymers. The review has been conceived to provide a useful tool for the researchers who are new to this field, as well as to offer an updated overview for those who are already actively working on this topic. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41141.
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Multilayered covalently supported ionic liquid catalysts achieve excellent TON and productivity in the reaction of CO2 with various epoxides to produce cyclic carbonates.
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ABSTRACT In view of investigating the possibility of cogeneration of chemicals and electricity in a fuel cell type reactor, a suitable electrocatalyst and optimal reaction conditions have to be found. The nitrobenzene reduction was taken... more
ABSTRACT In view of investigating the possibility of cogeneration of chemicals and electricity in a fuel cell type reactor, a suitable electrocatalyst and optimal reaction conditions have to be found. The nitrobenzene reduction was taken as the case study reaction for this investigation. In literature no suitable electrocatalyst has been found for this reaction. Pt and Cu nanoparticles, supported by multiple wall carbon nanotubes, were taken as electrocatalysts and ethanolic and acidic ethanolic environments were studied as possible reaction media. The Cu nanoparticle catalyst displayed superior electrocatalytic behaviour since less overpotential is needed for the nitrobenzene reduction in both ethanolic and acidic ethanolic environment. The acidic ethanolic conditions were superior to the ethanolic conditions as less overpotential was required for the nitrobenzene reduction reaction and a higher conversion of nitrobenzene is obtained. In acidic ethanolic environment, a four-electron reduction is taking place, which was assigned to the reduction of nitrobenzene into phenylhydroxylamine. This compound is re-oxidised into nitrosobenzene when the solution comes into contact with oxygen, and the formed nitrosobenzene selectively reacts with another phenylhydroxylamine molecule, yielding azoxybenzene. The latter is an important compound in organic synthesis.