Polymer-supported phosphoramidites: highly efficient and recyclable catalysts for asymmetric hydrogenation of dimethylitaconate and dehydroamino acids and esters

Several novel phosphoramidites have been prepared by reaction of the primary amines para-vinylaniline, ortho-anisidine, 2-methoxyphenyl(4-vinylbenzyl)amine, 8-aminoquinoline and 3-vinyl-8-aminoquinoline with (S)-1,1'-bi-2-naphthylchlorophosphite, in the presence of base. Rhodium(l) complexes of these phosphoramidites catalyse the asymmetric hydrogenation of dimethylitaconate and dehydroamino acids and esters giving ee values up to 95%. Soluble non-cross linked polymers of the para-vinylaniline and 3-vinyl-8-aminoquinoline-based phosphoramidites have been prepared by free radical co-polymerisation with styrene in the presence of AIBN as initiator. The corresponding [Rh(COD)](+) complexes serve as recyclable catalysts for the asymmetric hydrogenation dimethylitaconate and dehydroamino acids and esters to give ee values up to 80%. (C) 2003 Elsevier Science Ltd. All rights reserved.

In situ XAFS investigation of palladium species present during the Heck reaction in room temperature ionic liquids

The Heck reaction, performed in room temperature ionic liquids, has been studied by in situ XAFS, which indicates that palladium clusters of 0.8-1.6 nm diameter are the main species present during reaction.

Catalytic role of gold in gold-based catalysts: A density functional theory study on the CO oxidation on gold

Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO2 has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O-2 dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O-2 dissociation on Au (O-2-->20(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O-2 on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O-2 can adsorb on the interface of Au/TiO2 with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O-2 dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O-2-->CO2+O, and CO+O-->CO2; and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N-2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts.

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

The effect of SO2 on the activity of Pd-based catalysts in methane combustion

The effect of SO2 on Pd-based catalysts for the combustion of methane has been investigated. It is shown that while SO2 poisons Al2O3- and SiO2-supported catalysts. pre-treatment of Pd/ZrO2 by SO2 enhances the activity substantially.

The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol

A series of Cu-zirconia catalysts containing various additives (Y2O3, La2O3, Al2O3 and CeO2) have been prepared by coprecipitation and their activities and stabilities under operating conditions have been obtained for the steam reforming of methanol. It has been found that an yttria-promoted catalyst containing 30 mol% Cu and 20 mol% of Y2O3 is not only very active but is also very stable under reaction conditions. The yttria appears to stabilise a high copper surface area and may also have a slight promotional effect on the copper. The results obtained with this material compare very favourably with data for the best catalysts reported in the literature. (C) 2007 Published by Elsevier B.V.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

A new approach for the detection of ethylene using silica-supported palladium complexes

The coordination of olefins to square-planar Pd(II) and Pt(II) complexes containing 2,9-dimethylphenanthroline (L1) often involves a change of color associated with a change of geometry at the metal center. In order to obtain suitable colorimetric detectors for ethylene gas, a series of new Pd(II) and Pt(II) compounds with a range of 2,9-disubstituted phenanthroline ligands [2,9-di-n-butyl-1,10-phenanthroline (L-2), 2,9-di-s-butyl-1,10-phenanthroline (L3), 2,9-diphenyl-1,10-phenanthroline (L4), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, L5)] have been prepared and their reactivity toward ethylene investigated both in solution and after depositing the detector compounds on a variety of solid supports. The Pd(II) complex [PdCl2(L2)] supported on silica undergoes a clear color change upon exposure to ethylene, while remaining stable toward air and water, and forms the basis for new simple colorimetric detectors with potential applications in ethylene pipe-leak detection and the monitoring of fruit ripening. Encouragingly, the detector is able to discriminate between fruit at different stages of ripening. The response of the detector to other volatiles was also examined, and specific color changes were also observed upon exposure to aromatic acetylenes. The crystal structures of four new derivatives, including the ethylene-Pt(II) complex [PtCl2(C2H4)(L2)], are also described.

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.

Gold imidazolium-based ionic liquids, efficient catalysts for cycloisomerization of gamma-acetylenic carboxylic acids

Ionic liquid stabilized gold(III) chloride is shown to be a very active catalyst in the cyclization of sterically hindered and unhindered acetylenic carboxylic acid substrates even in the absence of a base.