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Claudio Evangelisti

    Claudio Evangelisti

    A simple and reproducible approach for the synthesis of Cu-based heterogeneous catalysts, named flow chemisorption hydrolysis (flow-CH), is reported. The approach, derived from the CH method, allows size-controlled CuO nanoparticles (mean... more
    A simple and reproducible approach for the synthesis of Cu-based heterogeneous catalysts, named flow chemisorption hydrolysis (flow-CH), is reported. The approach, derived from the CH method, allows size-controlled CuO nanoparticles (mean diameter 2.9 nm) to be obtained, that are highly and homogeneously dispersed into hierarchically meso-/macroporous silica monoliths. The Cu-based monolithic catalysts (CuO@SiO2-MN, 8.4 wt.% Cu) were studied in the styrene oxide ring opening reaction at 60 °C in the presence of isopropanol, under continuous flow-through conditions. A remarkable activity with a steady-state conversion of 97% for 13 h and 100% selectivity towards the corresponding β-alkoxyalcohol was observed. The performances of CuO@SiO2-MN were higher than those obtained in batch conditions with the previously reported CuO/SiO2 catalysts and with the ground CuO@SiO2-MN monolith in terms of productivity and selectivity. Moreover, a negligible Cu leaching (<0.6 wt.%) in reaction me...
    Any release of radioactive cesium-137, due to unintentional accidents in nuclear plants, represents a dangerous threat for human health and the environment. Prussian blue has been widely studied and used as an antidote for humans exposed... more
    Any release of radioactive cesium-137, due to unintentional accidents in nuclear plants, represents a dangerous threat for human health and the environment. Prussian blue has been widely studied and used as an antidote for humans exposed to acute internal contamination by Cs-137, due to its ability to act as a selective adsorption agent and to its negligible toxicity. In the present work, the synthesis protocol has been revisited avoiding the use of organic solvents to obtain Prussian blue nanoparticles with morphological and textural properties, which positively influence its Cs+ binding capacity compared to a commercially available Prussian blue sample. The reduction of the particle size and the increase in the specific surface area and pore volume values compared to the commercial Prussian blue reference led to a more rapid uptake of caesium in simulated enteric fluid solution (+35% after 1 h of contact). Then, after 24 h of contact, both solids were able to remove >98% of the...
    Polymer‐supported PdCu alloy nanoparticles with a palladium to copper atom ratio of 1 have been synthesized upon: (i) Coordination of palladium/copper acetate to 2,2’‐bipyridine‐end functionalized poly(lactic acid) (PLA);... more
    Polymer‐supported PdCu alloy nanoparticles with a palladium to copper atom ratio of 1 have been synthesized upon: (i) Coordination of palladium/copper acetate to 2,2’‐bipyridine‐end functionalized poly(lactic acid) (PLA); (ii) Stereocomplexation of PLA‐based macrocomplexes of opposite stereochemistry, and (iii) metal reduction with hydrogen. The obtained supported PdCu nanoparticles were successfully applied in the semi‐hydrogenation of industrially important alkynols, such as 3‐hexyn‐1‐ol and 2‐butyne‐1,4‐diol leading to the corresponding cis‐alkenol in high selectivity (98 %) under mild reaction conditions (i. e. ethanol, T (25 °C), p(H2)=3 bar) in the absence of any further additive. From a comparison of the catalytic performance of supported PdCu nanoparticles with those of Pd and Cu, located in the same chemical environment, emerged a clear alloy effect (i. e. high chemoselectivity for the alkene at high alkyne conversion). Recycling experiments conducted with the PdCu‐based ca...
    Heterogeneous catalysis is an essential tool for the development of both emerging and established chemical processes, as well as for their economic and environmental sustainability [...]
    Supported catalysts are important tools for developing green-economy-based processes. Palladium nanoparticles (NPs) that are immobilized on two fibers developed as metal scavengers (i.e., Smopex®-234 and Smopex®-111, 1% w/w) have been... more
    Supported catalysts are important tools for developing green-economy-based processes. Palladium nanoparticles (NPs) that are immobilized on two fibers developed as metal scavengers (i.e., Smopex®-234 and Smopex®-111, 1% w/w) have been prepared and tested in copper-free cyclocarbonylative Sonogashira reactions. Their catalytic activity has been compared with that of a homogeneous catalyst (i.e., PdCl2(PPh3)2). Pd/Smopex®-234 showed high activity and selectivity in the synthesis of functionalized heterocycles, such as phthalans and isochromans, even when working with a very low amount of palladium (0.2–0.5 mol%). The extension of Pd/Smopex®-234 promoted cyclocarbonylative reactions to propargyl and homopropargyl amides afforded the corresponding isoindoline and dihydrobenzazepine derivatives. A preliminary test on Pd NPs leaching into the solution (1.7 × 10−3 mg) seems to indicate that, at the end of the reaction, almost all of the active metal is present on the fiber surface.
    Palladium nanoparticles stabilized by a sterically demanding secondary diamine ligand have been synthesized by hydrogen reduction of a palladium acetate complex bearing the corresponding diimine ligand. The obtained nanoparticles were... more
    Palladium nanoparticles stabilized by a sterically demanding secondary diamine ligand have been synthesized by hydrogen reduction of a palladium acetate complex bearing the corresponding diimine ligand. The obtained nanoparticles were used to catalyze the aerobic oxidation of 1,2‐propandiol in n‐hexane, and after their heterogenization onto a high surface area carbon, in water. In n‐hexane (2,4‐dimethyl‐1,3‐dioxolan‐2‐yl) methanol has been obtained as major product, whereas in water acetic acid with a selectivity of >85 % has been achieved. The selectivity switch observed was a clear induced by water. The robustness of diamine‐stabilized palladium nanoparticles under real aerobic oxidation conditions has been proved by recycling experiments, TEM measurements of the recovered catalysts and by comparison of its performance with that of palladium nanoparticles generated by the metal vapor synthesis technique and supported onto the same carbon in the absence of the stabilizing diamin...
    The lack of supported versions of the tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA) ligand, suitable for flow-chemistry applications at scale, prompted us to develop a new route for the immobilization of such tris-triazole... more
    The lack of supported versions of the tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA) ligand, suitable for flow-chemistry applications at scale, prompted us to develop a new route for the immobilization of such tris-triazole chelating units on highly cross-linked polystyrene resins. With this aim, the preparation of the known TBTA-type monomer 3 was optimized to develop a high-yield synthetic sequence, devoid of chromatographic purifications at any stage. Then, bead-type (P7) and monolithic (M7) functional resins were obtained by the easy and scalable suspension- or mold-copolymerization of 3 with divinylbenzene. Both types of materials were found to possess a highly porous morphology and specific surface area in the dry state and could be charged with substantial amounts of Cu(I) or Cu(II) salts. After treatment of the latter with a proper reducing agent, the corresponding supported Cu(I) complexes were tested in the copper-catalyzed alkyne-azide cycloaddition reaction (Cu...
    The substitution of complex hydrides and Ni- and noble metal-based catalysts in the synthesis of pharma and fragrance products is a relevant topic in the green chemistry scenario. Here, we report that non-toxic, non-noble metal-based... more
    The substitution of complex hydrides and Ni- and noble metal-based catalysts in the synthesis of pharma and fragrance products is a relevant topic in the green chemistry scenario. Here, we report that non-toxic, non-noble metal-based Cu/SiO2 catalysts are effective and very selective in the hydrogenation of α,β-unsaturated ketones, esters and sulfones under very mild conditions. Vanillyl acetone can be obtained in quantitative yield in 1 h at 90 °C and 1 bar of H2. High dispersion of the metallic phase and support wettability play a significant role in determining catalytic performance.
    Montmorillonite clay was modified to introduce iron species and acid sites in the interlayer space, aiming to obtain a catalyst with oxidising and acid properties for the degradation of chemical warfare agents.
    In this study, niobia-based materials have been used as supports for Pt nanoparticles and used in the hydrogenation of furfural. The incorporation of dopants (W6+ and Ti4+) in the Nb2O5 structure induced modifications in the surface... more
    In this study, niobia-based materials have been used as supports for Pt nanoparticles and used in the hydrogenation of furfural. The incorporation of dopants (W6+ and Ti4+) in the Nb2O5 structure induced modifications in the surface acidity of the support; in particular, the addition of W6+ increased the amount of Lewis acid sites, while the addition of Ti4+ decreased the number of Lewis acid sites. As a result, the catalytic activity towards the hydrogenation of furfural was affected; high surface acidity resulted in high catalytic activity. The selectivity of the reaction changed with the support acidity as well, with higher amount of furfuryl alcohol produced decreasing the Lewis acid sites.
    The synthesis, characterization and catalytic performance of a conceptually simple, novel NbOx-SiO2 catalyst are here described. The niobium(V)-silica catalyst was prepared starting from cheap and viable reactants, by alkaline deposition... more
    The synthesis, characterization and catalytic performance of a conceptually simple, novel NbOx-SiO2 catalyst are here described. The niobium(V)-silica catalyst was prepared starting from cheap and viable reactants, by alkaline deposition of NH4Nb(C2O4)2·H2O in the presence of fructose as a stabilizer and subsequent calcination. The NbOx-SiO2 solid (0.95 Nb wt.%) was tested in the liquid-phase epoxidation with aqueous hydrogen peroxide of methyl oleate, as a model substrate. It was then tested in the epoxidation of a mixture of methyl esters (FAMEs) obtained by transesterification with methanol and purification of karanja oil, extracted from the autochthonous Indian variety of Millettia pinnata tree. The catalyst showed a promising performance in terms of methyl oleate conversion (up to 75%) and selectivity to epoxide (up to 82%). It was then tested on the FAME mixture from karanja oil, where interesting conversion values were attained (up to 70%), although with lower selectivities a...
    The synthesis of N-heterocyclic carbene (NHC)-stabilized palladium nanoparticles (PdNPs) by an entirely new strategy comprising the NHC functionalization of ligand-free PdNPs obtained by metal vapor synthesis is described. Detailed... more
    The synthesis of N-heterocyclic carbene (NHC)-stabilized palladium nanoparticles (PdNPs) by an entirely new strategy comprising the NHC functionalization of ligand-free PdNPs obtained by metal vapor synthesis is described. Detailed characterization confirms the formation of very small monodisperse PdNPs (2.3 nm) and the presence of the NHC ligand on the Pd surface. The stable NHC-functionalized PdNPs dispersed onto a carbon support showed high activity in the hydrogenation of limonene with enhanced regioselectivity in comparison to bare PdNPs on carbon.
    CuPd bimetallic solvated metal atoms (SMA) synthesized by metal vapor synthesis (MVS) technique and supported on poly‐4‐vinylpyridine (PVPy) resin, showed significantly higher catalytic activity in Sonogashira‐type carbon–carbon coupling... more
    CuPd bimetallic solvated metal atoms (SMA) synthesized by metal vapor synthesis (MVS) technique and supported on poly‐4‐vinylpyridine (PVPy) resin, showed significantly higher catalytic activity in Sonogashira‐type carbon–carbon coupling reactions than the corresponding monometallic Cu and Pd systems as well as their physical mixture. The analysis of the bimetallic catalyst combining transmission electron microscopy techniques and X‐ray absorption fine structure (XAFS) spectroscopy revealed the presence of small Pd nanoparticles (dm=2.5 nm) while the analysis of the X‐ray absorption data, at the Cu K‐edge suggests the formation of thin and incomplete Cu oxide layers around the Pd‐rich cores.
    A one-pot one-step transformation of butanol into butyl butanoate takes place with excellent yield on a Cu/ZrO2 catalyst.
    Star-shaped gold nanoparticles (StarAuNPs) are extremely attractive nanomaterials, characterized by localized surface plasmon resonance which could be potentially employed in a large number of applications. However, the lack of a reliable... more
    Star-shaped gold nanoparticles (StarAuNPs) are extremely attractive nanomaterials, characterized by localized surface plasmon resonance which could be potentially employed in a large number of applications. However, the lack of a reliable and reproducible synthetic protocols for the production of StarAuNPs is the major limitation to their spreading. For the first time, here we present a robust protocol to manufacture reproducible StarAuNPs by exploiting a fluidic approach. Star-shaped AuNPs have been synthesized by means of a seed-less protocol, employing ascorbic acid as reducing agent at room temperature. Moreover, the versatility of the bench-top microfluidic protocol has been exploited to afford hydrophilic, hydrophobic and solid-supported engineered StarAuNPs, by avoiding intermediate NP purifications.
    Free and trioctylamine (TOA)-stabilized ruthenium nanoparticles have been prepared by decomposition of the metal precursor Ru(η6-cycloocta-1,3,5-triene)(η4-cycloocta-1,5-diene) under mild conditions (room temperature, hydrogen atmospheric... more
    Free and trioctylamine (TOA)-stabilized ruthenium nanoparticles have been prepared by decomposition of the metal precursor Ru(η6-cycloocta-1,3,5-triene)(η4-cycloocta-1,5-diene) under mild conditions (room temperature, hydrogen atmospheric pressure). The nanoparticles have been deposited on γ-Al2O3 supports having different surface area. The resulting systems are active in the hydrogenation of methyl benzoate to methyl cyclohexanoate with a reaction rate decreasing in the order Ru(TOA)/γ-Al2 O3
    ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select... more
    ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    Nanostructured titanium oxide difluoride embedded in a matrix of amorphous carbon was synthesized by pyrolysis of d-fructose in the presence of titanium tetrafluoride (optimal Ti/fructose molar ratio = 5.5), both in the solid state at ca.... more
    Nanostructured titanium oxide difluoride embedded in a matrix of amorphous carbon was synthesized by pyrolysis of d-fructose in the presence of titanium tetrafluoride (optimal Ti/fructose molar ratio = 5.5), both in the solid state at ca. 150 °C and in suspension of 1,2-dichloroethane at reflux temperature. The resulting solid materials were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and elemental analysis. In every case, PXRD and TEM data indicated the presence of an unique crystalline phase (TiOF2) embedded in a light matrix (amorphous carbon). The average crystal size of the powder can be regulated by varying the reaction time.
    Increasing attention is being paid to nanometer-scale metal particles; they are of great interest in several fields, ranging from material science and catalysis to biology [1]. Their behaviour is strongly related to the particle size... more
    Increasing attention is being paid to nanometer-scale metal particles; they are of great interest in several fields, ranging from material science and catalysis to biology [1]. Their behaviour is strongly related to the particle size distribution, and nanostructured metals ...
    The complexation of heptakis(6-deoxy-6-thio)cyclomaltoheptaose to gold nanoparticles prepared by using the Metal Vapour Synthesis (MVS) led to water soluble gold nanoaggregates, thermally stable at 25°C. The role of gold concentration in... more
    The complexation of heptakis(6-deoxy-6-thio)cyclomaltoheptaose to gold nanoparticles prepared by using the Metal Vapour Synthesis (MVS) led to water soluble gold nanoaggregates, thermally stable at 25°C. The role of gold concentration in the MVS-derived starting solution as well as of the cyclodextrin to gold molar ratio on the size of cyclodextrin-capped gold nanoparticles were investigated. The ability of cyclodextrin bonded to gold nanoparticles to include deoxycytidine was also probed in comparison with that of 1-thio-β-D-glucose sodium salt.
    ABSTRACT A procedure to synthesize new Au–Pd bimetallic catalysts using Au and Pd vapours as reagents (metal vapour synthesis, MVS) is reported. The simultaneous co-condensation of Au and Pd vapours with acetone vapour affords... more
    ABSTRACT A procedure to synthesize new Au–Pd bimetallic catalysts using Au and Pd vapours as reagents (metal vapour synthesis, MVS) is reported. The simultaneous co-condensation of Au and Pd vapours with acetone vapour affords Au–Pd/acetone-solvated metal atoms which have been used to deposit Au–Pd bimetallic nanoparticles on γ-alumina and titanium oxide supports. Transmission electron microscopy (TEM) analysis determined the nanoparticles dimensions (dm = 2.2–2.4 nm) and size distribution while the X-ray absorption spectroscopy (XAS) analysis showed the presence of small bimetallic Au–Pd nanoparticles with a large amount of Au–Pd bonds. The bimetallic co-condensed systems, tested in the selective oxidation of benzyl alcohol with molecular oxygen both in toluene solvent and in solvent-free conditions, showed higher catalytic activity and selectivity than the corresponding monometallic systems as well as of the analogous systems obtained by separate evaporation of the two metals.

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