Search results for "catalyst"
showing 10 items of 516 documents
The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
2016
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…
Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal…
2016
Metal nanoclusters whose surface ligands are removable while keeping their metal framework structures intact are an ideal system for investigating the influence of surface ligands on catalysis of metal nanoparticles. We report in this work an intermetallic nanocluster containing 62 metal atoms, Au34Ag28(PhC≡C)34, and its use as a model catalyst to explore the importance of surface ligands in promoting catalysis. As revealed by single-crystal diffraction, the 62 metal atoms in the cluster are arranged as a four-concentric-shell Ag@Au17@Ag27@Au17 structure. All phenylalkynyl (PA) ligands are linearly coordinated to the surface Au atoms with staple "PhC≡C-Au-C≡CPh" motif. Compared with reporte…
Organic synthesis of high added value molecules with MOF catalysts
2020
Recent examples of organic synthesis of fine chemicals and pharmaceuticals in confined spaces of MOFs are highlighted and compared with silica-based ordered porous solids, such as zeolites or mesoporous (organo)silica. These heterogeneous catalysts offer the possibility of stabilizing the desired transition states and/or intermediates during organic transformations of functional groups and (C-C/C-N) bond forming steps towards the desired functional high added value molecular scaffolds. A short introduction on zeolites, mesoporous silica and metal-organic frameworks is followed by relevant applications in which confined active sites in the pores promote single or multi-step organic synthesis…
Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water
2009
Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …
HC-SCR of NOx over Ag/alumina: a combination of heterogeneous and homogeneous radical reactions?
2005
Matrix isolation combined with EPR and FT-IR technique at low temperature has been used to study the gas phase species involved in HC-SCR over a highly active Ag/alumina catalyst. A combination of heterogeneous and homogeneous (radical) reactions is proposed to take place over a Ag/alumina catalyst during HC-SCR. Radicals of low molecular weight were trapped in a growing argon matrix behind the Ag/alumina catalyst. In the same matrix, cyanogen isocyanate was detected and is suggested to be a key intermediate for the formation of amines and ammonia via the hydrolysis of isocyanate species.
Electrolyte-driven electrochemical amplification by poly(thienylacetylene) encapsulated within Zeolite Y
2006
Electrochemical oxidation and reduction of poly(thienylacetylene) encapsulated inside zeolite Y (PTA@Y) exhibit with large anodic and cathodic doping currents with a significant reversibility. Thienyl groups lower the redox potential of polyacetylene chain whereas encapsulation stabilizes the resulting charged radical species blocking undesired post electron-transfer cross-link reactions. Size-exclusion effects associated produces an electrolyte-dependent amplification of currents recorded at PTA@Y-modified electrodes for electrochemical processes involving selected substrates in solution, namely, dinitrobiphenyl and benzidine. Keywords: Poly(thienylacetylene), Zeolite Y, Electrochemistry, …
Electrocarboxylation of benzyl chlorides at silver cathode at the preparative scale level
2008
Abstract The electrocarboxylation of benzyl chlorides to the corresponding carboxylic acids performed at silver cathodes was investigated both theoretically and experimentally in order to find the influence of the operative parameters on the selectivity and on the Faradic efficiency of the process. Theoretical considerations were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivity and Faradic yields higher than 80% and 70%, respectively, were obta…
Electrochemical chiral recognition by microparticle coatings of Pd complexes with bridging cyclometalated phosphines
2008
Abstract The palladium(II) dinuclear complex with bridging cyclometalated phosphines, {Pd2[μ-(C6H4)PPh2]2(μ-O2CCH3)2} (Pd2L2), having a paddlewheel structure, is reversibly oxidized in CH2Cl2 to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd2L2 in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd2L2 produces a significant stereoselective electrocatalytic activity with respect to the oxidation of l - and d -glutamic acid in alkaline media.
Tuning the Magnetic Properties of Carbon by Nitrogen Doping of Its Graphene Domains
2015
Here we present the formation of predominantly sp-coordinate carbon with magnetic- and heteroatom-induced structural defects in a graphene lattice by a stoichiometric dehalogenation of perchlorinated (hetero)aromatic precursors [hexachlorobenzene, CCl (HCB), and pentachloropyridine, NCCl (PCP)] with transition metals such as copper in a combustion synthesis. This route allows the build-up of a carbon lattice by a chemistry free of hydrogen and oxygen compared to other pyrolytic approaches and yields either nitrogen-doped or -undoped graphene domains depending on the precursor. The resulting carbon was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM…
Electrocatalysis of the oxidation of methylenedioxyamphetamines at electrodes modified with cerium-doped zirconias
2004
The catalytic effect of monoclinic and tetragonal cerium-doped zirconias (m-CexZr1−xO2 and t-CexZr1−xO2, 0<x<0.10, respectively), prepared from gel precursors, on the oxidation of methylenedioxyamphetamine (MDA) and methylenedioxymetamphetamine (MDMA) at pH 7.0 has been studied. Upon attachment of synthetic specimens to polymer film electrodes, an oxidation peak near to +1.05 V vs AgCl/Ag appears that is unaffected by chloride ions and common interfering compounds, namely, dopamine, norepinephrine and ascorbic acid. The catalytic effect appears to be strongly influenced by crystallinity of specimens and coordination of cerium, increasing from the amorphous starting material to t-CexZr1−xO2 …