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 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.

Increased Dispersion of Supported Gold during Methanol Carbonylation Conditions

The active site in supported gold catalysts for the carbonylation of methanol has been identified as dimers/trimers of gold which are formed from large gold particles >10 nm in diameter. Methyl iodide was found to be critical for this dispersion process and to maintain the catalyst in the active form. This study also shows that it may be possible to redisperse gold catalysts, in general, after reaction.

Ionic liquids as solvent and solvent additives for the synthesis of sol-gel materials

The ionic liquid (IL) 1-butyl-3-methylimidazolium chloride was used as a drying control chemical additive in the synthesis of silica sol-gel materials with and without methanol as a co-solvent. The resulting gels were characterized by using thermogravimetric analysis, differential scanning calorimetry, infrared spectroscopy and water sorption kinetics. Calcined gels were analyzed using scanning electron microscopy and nitrogen adsorption isotherms for surface area and pore volume determination. Non-calcined gels were monolithic and showed general cloudiness with lesser degrees observed at higher IL volumes. Calcinations resulted in the formation of powders with increased available surface area as the amount of IL volume was increased. This is consistent with an increase in respective pore volume but a general decrease in average pore size. The resulting materials exhibited conventional structural microdomains, in contrast to periodicity reported when other ionic liquids were used as templates.

Asymmetric rhodium carbene insertion into the Si-H bond: identification of new dirhodium(II) carboxylate catalysts using parallel synthesis techniques

Decomposition of methyl 2-diazophenylacetate in the presence of silanes and a chiral dirhodium(11) catalyst results in Si-H insertion of the intermediate carbenoid with varying degrees of enantioselectivity. New chiral dirhodium(11) carboxylate catalysts were identified using solution phase parallel synthesis techniques. (C) 2003 Elsevier Science Ltd. All rights reserved.

Competing O-H insertion and  -elimination in rhodium carbenoid reactions; synthesis of 2-alkoxy-3-arylpropanoates

Rhodium(II) carboxylate catalyzed decompn. of diazo esters 3 (shown as I) and PhCH2C(CO2Et)N2 4 in the presence of alcs. or water results in formation of 2-alkoxy- or 2-hydroxy-3-arylpropanoates, resp., by O-H insertion in competition with cinnamates by elimination; the ratio of insertion to elimination is dramatically affected by the carboxylate ligand on rhodium. Use of methanol-d as the alc. confirms that the alkene does not arise by elimination from the initial alkoxyester product.

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

Green synthesis of biodiesel using ionic liquids

This paper is a hybrid starting with an overview and history of biodiesel synthesis and finishing with a description with some of our latest unpublished data. Initially, we examine "green" ways of obtaining biodiesel using ionic liquids, which can have an acidic or basic functionality, and can function both as a solvent and catalyst for the (trans)esterification reaction to obtain biodiesel. Both animal and vegetable resources can be utilized as a resource for (trans)esterification reactions depending on the geographical area. Biodiesel is of great interest because it enables motor vehicle transport using a renewable resource, while reducing the amount of carbon dioxide from fossil fuels being released into the environment.

Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene

Pt-ceria catalysts present different surface chemistries depending on the preparation method and the pretreatment. The catalytic behavior of Pt/CeO2 catalysts in the hydrodechlorination of trichloroethylene (TCE) to ethylene was examined as a function of the pretreatment conditions and the noble metal precursor salts. Using FTIR and X-ray photoelectron spectroscopy, significant differences were observed in the surface properties of Pt/CeO2 prepared from the H2PtCl6 precursor after different pretreatment procedures (i.e.. reduction or oxidation-reduction). These surface changes are related to chloride residues from the synthesis. Strong changes were observed in the selectivity of the catalysts to ethylene depending on the pretreatment conditions. The 0.5%Pt/CeO2 catalyst showed a 13% selectivity toward ethylene after reduction, whereas alter oxidation, followed by reduction, the selectivity increased up to 85% at the same conversion level. This effect was only observed when a chloride-containing precursor was used in the preparation. In this way, it is demonstrated that the use of a Cl-containing Pt precursor and an air treatment prior to reduction strongly improves the ethylene selectivity of Pt-CeO2 dechlorination catalysts. This can be explained by formation or a CeOCl phase during the synthesis that decomposes upon air tempering, producing oxygen vacancies on the ceria support. We propose that these oxygen vacancies are active for cleaving off Cl from the TCE. Pt then supplies II to clean-off Cl as HCl. Reaction of TCE on Pt produces rather ethane, so Pt may be partly Cl-poisoned for the hydrodechlorination reaction but not for II, dissociation or CO adsorption.

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C5R'(4)(CH2)(2)PR2] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C5R'(4)(C2H4) with LiPR2. C5Et4HSiMe2CH2PMe2, was prepared from reaction of Li[C5Et4] with Me2SiCl2 followed by Me2PCH2Li. The lithium salts were reacted with [RhCl(CO)2]2,[IrCl(CO)3] or [Co-2(CO)(8)] to give [M(C5R'(4)(CH2) 2PR2)(CO)] (M = Rh, R = Et, R' = H or Me, R= Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH2)(2)PEt2)(CO)] (Cp' = C5Me4), the most electron rich of the complexes. [Rh(C5Et4SiMe2CH2PMe2)(CO)] may be a dimer. [Co-2(CO)(8)] reacts with C5H5(CH2)(2)PEt2 or C5Et4HSiMe2CH2PMe2 (L) to give binuclear complexes of the form [Co-2(CO)(6)L-2] with almost linear PCoCoP skeletons. [Rh(Cp'(CH2)(2)PEt2)(CO)] and [Rh(Cp'(CH2)(2)PPh2)(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH2)(2)PPh2)(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI2(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH2)(2)PEt2)(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt3)(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH2)(2)PEt2)I-2], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH2)(2)PEt2)(CO)].

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.

Tetrahexahedral Pt Nanocrystal Catalysts Decorated with Ru Adatoms and Their Enhanced Activity in Methanol Electrooxidation

Tetrahexahedral Pt nanocrystals (THH Pt NCs) bound by well-defined high index crystal planes offer exceptional electrocatalytic activity, owing to a high density of low-coordination surface Pt sites. We report, herein, on methanol electrooxidation at THH Pt NC electrodes studied by a combination of electrochemical techniques and in situ FTIR spectroscopy. Pure THH Pt NC surfaces readily facilitate the dissociative chemisorption of methanol leading to poisoning by strongly adsorbed CO. Decoration of the stepped surfaces by Ru adatoms increases the tolerance to poisoning and thereby reduces the onset potential for methanol oxidation by over 100 mV. The Ru modified THH Pt NCs exhibit greatly superior catalytic currents and CO2 yields in the low potential range, when compared with a commercial PtRu alloy nanoparticle catalyst. These results are of fundamental importance in terms of model nanoparticle electrocatalytic systems of stepped surfaces and also have practical significance in the development of surface tailored, direct methanol fuel cell catalysts.

Effect of precursor on the performance of alumina for the dehydration of methanol to dimethyl ether

Dimethyl ether (DME) is amongst one of the most promising alternative, renewable and clean fuels being considered as a future energy carrier. In this study, the comparative catalytic performance of γ-Al2O3 prepared from two common precursors (aluminum nitrate (AN) and aluminum chloride (AC)) is presented. The impact of calcination temperature was evaluated in order to optimize both the precursor and pre-treatment conditions for the production of DME from methanol in a fixed bed reactor. The catalysts were characterized by TGA, XRD, BET and TPD-pyridine. Under reaction conditions where the temperature ranged from 180 °C to 300 °C with a WHSV = 12.1 h−1 it was found that all the catalysts prepared from AN(η-Al2O3) showed higher activity, at all calcination temperatures, than those prepared from AC(γ-Al2O3). In this study the optimum catalyst was produced from AN and calcined at 550 °C. This catalyst showed a high degree of stability and had double the activity of the commercial γ-Al2O3 or 87% of the activity of commercial ZSM-5(80) at 250 °C.

Activity and deactivation studies for direct dimethyl ether synthesis using CuO-ZnO-Al2O3 with NH(4)ZSM-5, HZSM-5 or gamma-Al2O3

Herein we investigate the use of CuO-ZnO-Al2O3 (CZA) with different solid acid catalysts (NH(4)ZSM-5. HZSM-5 or gamma-Al2O3) for the production of dimethyl ether from syngas. It was found that of the solid acids, which are necessary for the dehydration function of the admixed system, the CZA/HZSM-5 bifunctional catalyst with a 0.25 acid fraction showed high stability over a continuous period of 212 h.

As this particular system was observed to loose around 16.2% of its initial activity over this operating period this study further investigates the CZA/HZSM-5 bifunctional catalyst in terms of its deactivation mechanisms. TPO investigations showed that the catalyst deactivation was related to coke deposited on the metallic sites: interface between the metallic sites and the support near the metal-support: and on the support itself. 

Hierarchical zeolites prepared by organosilane templating: A study of the synthesis mechanism and catalytic activity

The crystallization of hierarchical ZSM-5 in the presence of the organosilane octadecyl-dimethyl-(3-trimethoxysilyl-propyl)-ammonium chloride as the mesoporogen was investigated as a function of time and temperature. The synthesis by this method proceeds in two steps. The rapid formation of a predominantly amorphous disordered mesoporous aluminosilicate precursor phase is followed by the formation of globular highly mesoporous zeolite particles involving dissolution of the precursor phase. It is difficult to completely convert the initial phase into the final hierarchical zeolite. This limits the amount of aluminium built into the MFI network and the resulting Bronsted acidity. In the presence of iron, more crystalline hierarchical zeolite is obtained. These Fe-containing zeolites are excellent catalysts for the selective oxidation of benzene to phenol. Their hierarchical pore structure leads to higher reaction rates due to increased mass transfer and increased catalyst longevity despite more substantial coke formation. (C) 2011 Elsevier B.V. All rights reserved.