Entrapping homogeneous catalysts by sol-gel methods: the bottom-up synthesis of catalysts that recycle and cascade

Perspective and front cover article: Homogeneous catalysts entrapped in silica matrices, including ionic liquid containing 'ionogels', exhibit high selectivity, unexpected activity and excellent recyclability.

The Co-Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol-gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co-entrapped with the ionic liquid [Bmim]NTf(2) inside a silica matrix by a sot-gel method. These catalytic ionogels have been compared to simple catalyst-doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh-doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X-ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.

Selective homogeneous snythesis of dimethyl ether from methanol

Selected Bronsted acidic ionic liquids were tested as homogeneous catalysts for the dehydration of methanol to dimethyl ether. Ionic liquids incorporating an alkanesulfonic acid as a part of the cation, a complex acidic anion, [A(2)H](-), or both, proved to be good catalysts for this process, providing high conversions and selectivities. Homogeneous catalysis in the liquid state represents a novel approach to dimethyl ether synthesis.

CsF and alumina: A mixed homogeneous-heterogeneous catalytic system for the transesterification of sunflower oil with methanol

The activity and nature (i e heterogeneous and/or homogeneous) of catalysts based on CsF supported on alpha-Al2O3 were investigated for the transesterification of vegetable oil with methanol. The effect of the activation temperature, CsF loading and the reusability in a recirculating reactor were first studied CsF/alpha-Al2O3 exhibited the highest activity for a CsF loading of 0 6 mmol/g and when activated at 120 degrees C An important aspect of this study is the effect of CsF leaching into the reaction mixture, which is attributed to the high solubility of CsF in methanol, leading to a complete loss of activity after one run It was Identified that the activity of the catalyst resulted from a synergy between alumina and dissolved CsF, the presence of both compounds being absolutely necessary to observe any conversion The use of an alumina with a higher surface area resulted in a far greater reaction rate, showing that the concentration of surface site on the oxide (probably surface hydroxyl) was rate-limiting in the case of the experiments using the low surface area alpha-Al2O3 This work emphasizes that combined homogeneous-heterogeneous catalytic systems made from the blending of the respective catalysts can be used to obtain high conversion of vegetable oil to biodiesel. Despite the homogeneous/heterogeneous dual character, such a catalytic system may prove valuable in developing a simple and cost-effective continuous catalytic process for biodiesel production (C) 2010 Elsevier B V All rights reserved

DECOMPOSITION PRODUCTS OF TRINUCLEAR RUTHENIUM COMPLEXES AS EFFECTIVE CATALYSTS OF WATER OXIDATION

Ruthenium red, a di-mu-oxo-bridged ruthenium complex, and its oxidised form, ruthenium brown, have been studied as possible homogeneous redox catalysts for the oxidation of water to O2 by Ce(IV) ions in H2SO4 and HCIO4. In both media the Ce(IV) ions oxidised the ruthenium red to brown and, with excess of Ce(IV), decomposed the ruthenium brown irreversibly to product(s) with three weak absorption bands at 390, 523 and 593 nm. Only in HCIO4 did the decomposition product(s) appear to act as a stable O2 catalyst. Spectral evidence tentatively suggests that the active catalyst may be a hydrolysed Ru(IV) polymeric species. The rate of catalysis was proportional to the initial concentration of ruthenium red/brown and the activation energy was determined as 36 +/- 1 kJ mol-1 over the temperature range ambient to ca. 50-degrees-C. At temperatures greater than 50-degrees-C the O2 catalyst undergoes an irreversible thermal decomposition reaction.

Chiral supported ionic liquid phase (CSILP) catalysts for greener asymmetric hydrogenation processes

Chiral supported ionic liquid phase (CSILP) catalysts were prepared by physical adsorption (within highly porous carbons or mesoporous silica) of Ir, Ru and Rh complexes as IrCl(COD)-(S, S)-BDPP, [IrCl-(S)-BINAP](2), RuCl(p-cymene)[(S, S)-Ts-DPEN], RuOTf(p-cymene)[(S, S)-Ts-DPEN], [Rh(COD)(S, S)-DIPAMP][BF4], and [Rh(COD)(R, R)-Me-DuPHOS][BF4]. For the syntheses of CSILP catalysts [EMIM][NTf2], [BMIM][BF4] and [BMIM][PF6] ionic liquids were used. Comparative homogeneous and heterogeneous experiments were carried out using the asymmetric hydrogenation of double -C N- and -C C- bonds in trimethylindolenine, 2-methylquinoline and dimethylitaconate, respectively. The conversion and enantioselectivity was found to depend on the nature of the complex (metal and ligand), the immobilization method used, nature of the ionic liquid, nature of the support and the experimental conditions. (C) 2012 Elsevier B.V. All rights reserved.

Measurement of oxygen storage capacity in automotive catalysts

There is considerable disagreement in the literature on available oxygen storage capacity, and on the reaction rates associated with the storage process, for three-way automotive catalysts. This paper seeks to address the issue of oxygen storage capacity in a clear and precise manner. The work described involved a detailed investigation of oxygen storage capacity in typical samples of automotive catalysts. The capacity has also been precisely defined and estimates have been made of the specific capacity based on catalyst dimensions. A purpose-built miniature catalyst test rig has been assembled to allow measurement of the capacity and the experimental procedure has been developed to ensure accurate measurement. The measurements from the first series of experiments have been compared with the theoretical calculations and good agreement is seen. A second series of experiments allowed the effect of temperature on oxygen storage capacity to be investigated. This work shows very clearly the large variation of the capacity with temperature.