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Inorganic Supports (inorganic + support)
Selected AbstractsChemInform Abstract: Asymmetric Dihydroxylation of Olefins Using Cinchona Alkaloids on Highly Ordered Inorganic Supports.CHEMINFORM, Issue 46 2001Irina Motorina Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 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. [source] An Efficient Hybrid, Nanostructured, Epoxidation Catalyst: Titanium Silsesquioxane,Polystyrene Copolymer Supported on SBA-15CHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2007Lei Zhang Abstract A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380,m2,g,1) and pore volume (,0.46,cm3,g,1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert -butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites. [source] The Immobilization of Rhodium-4-(diphenylphosphino)-2- (diphenylphosphinomethyl)-pyrrolidine (Rh-PPM) Complexes: A Systematic StudyADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006Benoît Pugin Abstract A modular toolbox for the immobilization of homogeneous catalysts to various supports is described. It consists of functionalized chiral diphosphines and three different linkers based on isocyanate chemistry and it is used to attach the 4-(diphenylphosphino)-2-(diphenylphosphinomethyl)-pyrrolidine (PPM) ligand to a large variety of soluble, swellable and non-swellable solid organic polymers and to silica gels. As model reaction the hydrogenation of acetamidocinnamic acid derivatives, catalyzed with high enantioselectivity was chosen. Besides information on the usefulness of a particular type of support for synthetic applications, the experiments were also designed to address the question how parameters such as solubility, swellability, cage or pore size and solvent affect the rate and enantioselectivity of an immobilized catalyst. Rhodium complexes of ligands attached to soluble polymers and inorganic supports achieved ees up to 95,% and turnover frequencies between 700 and 1400,h,1, very close to the values of the homogeneous Rh catalyst (ee 95,%, TOF 1320,h,1). Insoluble or strongly cross-linked organic polymers led to catalysts with lower enantioselectivity and activity. PPM ligands attached to water soluble dendrimer fragments allowed hydrogenation in water solution with ees up to 94,%, albeit with much lower activity compared to reactions in methanol with the homogeneous catalyst. [source] Influence of supported vanadium catalyst on ethylene polymerization reactionsPOLYMER INTERNATIONAL, Issue 2 2008Sutapa Ghosh Abstract BACKGROUND: In the research area of homogeneous Ziegler,Natta olefin polymerization, classic vanadium catalyst systems have shown a number of favourable performances. These catalysts are useful for (i) the preparation of high molecular weight polymers with narrow molecular weight distributions, (ii) the preparation of ethylene/R -olefin copolymers with high R -olefin incorporation and (iii) the preparation of syndiotactic polypropylenes. In view of the above merits of vanadium-based catalysts for polymerization reactions, the development of well-defined single-site vanadium catalysts for polymerization reactions is presently an extremely important industrial goal. The main aim of this work was the synthesis and characterization of a heterogeneous low-coordinate non-metallocene (phenyl)imido vanadium catalyst, V(NAr)Cl3, and its utility for ethylene polymerization. RESULTS: Imido vanadium complex V(NAr)Cl3 was synthesized and immobilized onto a series of inorganic supports: SiO2, methylaluminoxane (MAO)-modified SiO2 (4.5 and 23 wt% Al/SiO2), SiO2 Al2O3, MgCl2, MCM-41 and MgO. Metal contents on the supported catalysts determined by X-ray fluorescence spectroscopy remained between 0.050 and 0.100 mmol V g,1 support. Thermal stability of the catalysts was determined by differential scanning calorimetry (DSC). Characterization of polyethylene was done by gel permeation chromatography and DSC. All catalyst systems were found to be active in ethylene polymerization in the presence of MAO or triisobutylaluminium/MAO mixture (Al/V = 1000). Catalyst activity was found to depend on the support nature, being between 7.5 and 80.0 kg PE (mol V),1 h,1. Finally, all catalyst systems were found to be reusable for up to three cycles. CONCLUSION: Best results were observed in the case of silica as support. Acid or basic supports afforded less active systems. In situ immobilization led to higher catalyst activity. The resulting polyethylenes in all experiments had ultrahigh molecular weight. Finally, this work explains the synthesis and characterization of reusable supported novel vanadium catalysts, which are useful in the synthesis of very high molecular weight ethylene polymers. Copyright © 2007 Society of Chemical Industry [source] Oxidant-Free Dehydrogenation of Alcohols Heterogeneously Catalyzed by Cooperation of Silver Clusters and Acid,Base Sites on AluminaCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2009Ken-ichi Shimizu Dr. Abstract Trifunctional green catalysis: In-depth characterization shows that oxidant-free selective oxidation of alcohols by silver nanoparticles on ,-Al2O3, as a new heterogeneous catalyst, proceeds through cooperation of silver, acid, and base sites (see figure). A ,-alumina-supported silver cluster catalyst,Ag/Al2O3,has been shown to act as an efficient heterogeneous catalyst for oxidant-free alcohol dehydrogenation to carbonyl compounds at 373,K. The catalyst shows higher activity than conventional heterogeneous catalysts based on platinum group metals (PGMs) and can be recycled. A systematic study on the influence of the particle size and oxidation state of silver species, combined with characterization by Ag,K-edge XAFS (X-ray absorption fine structure) has established that silver clusters of sizes below 1,nm are responsible for the higher specific rate. The reaction mechanism has been investigated by kinetic studies (Hammett correlation, kinetic isotope effect) and by in situ FTIR (kinetic isotope effect for hydride elimination reaction from surface alkoxide species), and the following mechanism is proposed: 1),reaction between the alcohol and a basic OH group on the alumina to yield alkoxide on alumina and an adsorbed water molecule, 2),CH activation of the alkoxide species by the silver cluster to form a silver hydride species and a carbonyl compound, and 3),H2 desorption promoted by an acid site in the alumina. The proposed mechanism provides fundamental reasons for the higher activities of silver clusters on acid,base bifunctional support (Al2O3) than on basic (MgO and CeO2) and acidic to neutral (SiO2) ones. This example demonstrates that catalysts analogous to those based on of platinum group metals can be designed with use of a less expensive d10 element,silver,through optimization of metal particle size and the acid,base natures of inorganic supports. [source] | ||||||||||