Electrochemical promotion of a platinum catalyst supported on the high-temperature proton conductor La0.99Sr0.01NbO4-δ

The recently discovered, high-temperature proton conductor, La_0.99Sr_0.01NbO_4-δ, was used as a support for the electrochemical promotion of a platinum catalyst. Ethylene oxidation was used as a probe reaction in the temperature range 350-450 °C. Moderate non-Faradaic rate modification, attributable to a protonic promoting species, occurred under negative polarisation; some permanent promotion was also observed. In oxidative atmospheres, both the p_O2 of the reaction mixture and the temperature influenced the type and magnitude of the observed rate modification. Rate-enhancement values of up to ρ = 1.4 and Faradaic-efficiency values approaching Λ = -100 were obtained. Promotion was observed under positive polarisation and relatively dry, oxygen-rich atmospheres suggesting that some oxygen ion conductivity may occur under these conditions. Impedance spectroscopy performed in atmospheres of 4 kPa O₂/N₂ and of 5 kPa H₂/N₂ under dry and slightly humidified (0.3 kPa H₂O) conditions indicated that the electrical resistivity is heavily dominated by the grain-boundary response in the temperature range of the EPOC studies; much lower grain-boundary impedances in the wetter conditions are likely to be attributable to proton transport. © 2009 Elsevier B.V. All rights reserved.

Remote control of the activity of a Pt catalyst supported on a mixed ionic electronic conducting membrane

A novel configuration for the in situ control of the catalytic activity of a polycrystalline Pt catalyst supported on a mixed ionic electronic conducting (MIEC) substrate is investigated. The modification of the catalytic activity is achieved by inducing the reverse spillover of oxygen promoting species from the support onto the catalyst surface, thus modifying the chemisorptive bond energy of the gas phase adsorbed reactants. This phenomenon is known as Electrochemical Promotion of Catalysis (EPOC). In this work we investigate the use of a wireless system that takes advantage of the mixed ionic electronic conductivity of the catalyst support (internally short-circuiting the system) in a dual chamber reactor. In this wireless configuration, the reaction takes place in one chamber of the membrane reactor while introduction of the promoting species is achieved by the use of an appropriate sweep gas (and therefore control of the oxygen chemical potential difference across the membrane) on the other chamber. Experimental results have shown that the catalytic rate can be enhanced by using an oxygen sweep, while a hydrogen sweep can reverse the changes. Total rate enhancement ratios of up to 3.5 were measured. © 2008 Elsevier B.V. All rights reserved.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

Electrochemical promotion of a metal catalyst supported on a mixed-ionic conductor

It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr_0.9Y_0.1O_{3 - α} (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.

Modulating the selectivity for CO and butane oxidation over heterogeneous catalysis through amorphous catalyst coatings

The preparation of porous films directly deposited onto the surface of catalyst particles is attracting increasing attention. We report here for the first time a method that can be carried out at ambient pressure for the preparation of porous films deposited over 3 mm diameter catalyst particles of silica-supported Pt-Fe. Characterization of the sample prepared at ambient pressure (i.e., open air, OA) and its main structural differences as compared with a Na-A (LTA) coated catalyst made using an autoclave-based method are presented. The OA-coated material predominantly exhibited an amorphous film over the catalyst surface with between 4 and 13% of crystallinity as compared with fully crystallized LTA zeolite crystals. This coated sample was highly selective for CO oxidation in the presence of butane with no butane oxidation observed up to 350 degrees C. This indicates, for the first time, that the presence of a crystalline membrane is not necessary for the difference in light off temperature between CO and butane to be achieved and that amorphous films may also produce this effect. An examination of the space velocity dependence and adsorption of Na+ on the catalysts indicates that the variation in CO and butane oxidation activity is not caused by site blocking predominantly, although the Pt activity was lowered by contact with this alkali.

CO multipulse TAP studies of 2% Pt/CeO2 catalyst: Influence of catalyst pretreatment and temperature on the number of active sites observed

CO multipulse temporal analysis of products (TAP) experiments were used to characterize a ceria-supported platinum catalyst after various oxidative and reductive pretreatments using O-2, H2O, CO2, and H-2. Based on the amount of CO consumed, using the final CO-saturated catalyst composition as the common state point, the oxidatively pretreated catalyst could be described using a general scale. From a kinetic analysis of the CO multipulse responses, two kinetic regimes corresponding to two types of active sites could be identified. As the temperature was raised, the number of the most active sites did not change while the amount of the less active site increased. Comparison of the number of active sites determined from the TAP data reported herein with that determined by a previous steady-state isotope transient kinetic analysis experiment showed excellent agreement. This correlation indicates that the (very fast response) TAP experiments can provide information regarding the number and type of active sites that are relevant to a catalyst under real reaction conditions. (c) 2007 Elsevier Inc. All rights reserved.

Efficient heterogeneous asymmetric catalysis of the Mukaiyama aldol reaction by silica- and ionic liquid-supported Lewis acid copper(II) complexes of bis(oxazolines)

Lewis acid complexes based on copper(II) and an imidazolium-tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1-methoxy-1-tri-methylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2 min compared with only 55% conversion after 60 min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3-hydroxy-1,3-diphenylbutan-1-one as a by-product. Supporting the catalyst on silica or an imidazolium-modified silica using the ionic liquid or in an ionic liquid-diethyl ether system completely suppressed the formation of this by-product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee.

Supported and liquid phase task specific ionic liquids for base catalysed Knoevenagel reactions

A series of Hunig's base tethered ammonium ionic liquids have been used to catalyse the Knoevenagel condensation of aldehydes/ketones with malononitrile and ethyl cyanoacetate. The reactions were performed under homogeneous and under biphasic, liquid-liquid and liquid-silica supported ionic liquid, conditions with the biphasic systems employing cyclohexene as the second phase. By increasing the distance between the ammonium head group and Hunig's base the activity of the catalyst was found to increase. Higher activity, in general, was found under homogeneous reaction conditions; however, the recyclability of the catalyst was improved by supporting the BIL under biphasic conditions. (c) 2007 Elsevier B.V. All rights reserved.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (

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.

Characteristics of RuCl2(CHPh)(PCy3)(2) as a catalyst for ring-opening metathesis polymerization

Ring-opened metathesis polymers and copolymers have been formed from norbornene, norbornadiene, a range of their derivatives, and cyclopentene using RuCl2(CHPh)(PCy3)(2), as catalyst. C-13 NMR analysis of the polymers illustrate a rather selective propagation reaction. The catalyst is highly regioselective, and the polymers are generally high trans with a strong isotactic bias. However, polymers from diene monomers tend to be less isotactic than those from the corresponding monoenes, and in the case of 7-methylnorbornadiene the polymer has an overall syndiotactic bias. A rate enhancing effect, noted previously, due to an oxygen atom proximate to the monomer double bond, is less pronounced than with other initiators. Catalyst activity, in the case of certain diene monomers, was shown to be monomer dependent and rate enhancements were also achieved using phenol as solvent. The results are interpreted in terms of the steric and electronic properties of both the catalyst and the monomers.

Highly selective and efficient hydrogenation of carboxylic acids to alcohols using titania supported Pt catalysts

Selective hydrogenation of carboxylic acids to alcohols and alkanes has been achieved under remarkably mild reaction temperatures and H-2 pressures (333 K, 0.5 MPa) using Pt/TiO2 catalyst.

Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.

A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph2P(3-C6H4SO3)] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf2 (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF3SO2) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO2. Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas: substrate ratio. However, a factor-dependent interaction between the syngas: substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO2 pressures or when N-2 was used instead of CO2 rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO2 pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the catalyst was not much affected by the variation of process parameters. The linear: branched (1:b) ratios were ca. 3, similar to that obtained using the very same catalyst in conventional organic solvents.

Selective oxidation of a pyrimidine thioether using supported tantalum catalysts

Ta2O5-SiO2 catalysts were prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) and tantalum (V) ethoxide as the sources of silicon and tantalum, and two families of quaternary ammonium salts, [CnH(2n+1)(CH3)(3)N]Br (n = 14, 16, 18) and [(CnH(2n+1))(4)N]Br (n = 10, 12, 16, 18) as surfactants. The catalysts were compared for the selective suffoxidation of 4,6-dimethyl-2-thiomethylpyrimidine using peroxide as an oxidising agent in a range of ionic liquids and organic solvents. The sol-gel catalysts were also compared with tantalum on MCM-41 prepared by grafting. The catalysts were characterized from adsorption-desorption isotherms of N-2, XRD patterns, small-angle X-ray scattering, IR spectra from adsorbed pyridine and CDCl3, XPS spectra, and Si-29 magic angle spinning (MAS) NNIR experiments. The effect of recycling on the catalyst leaching and selectivity/activity was also studied. High activities and selectivities were found in [NTf2](-) based ionic liquids and organic solvents with good recyclability of the catalyst. Tantalum was found in the solution after reaction; however, this was determined to be due to entrapment of catalyst particulates, as opposed to leaching of the active metal. (c) 2005 Elsevier Inc. All rights reserved.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).