A modified commercial DRIFTS cell for kinetically relevant operando studies of heterogeneous catalytic reactions

This paper discusses a number of checks that should be carried out to ensure that the kinetic and spectroscopic measurements made using a DRIFTS cell are meaningful. The observations reported here demonstrate how an appropriately modified commercial DRIFTS cell can provide pertinent kinetic information about both gaseous products and the related surface intermediates. The oxidation of CO with 02 was used as a test to assess the catalyst bed bypass by the reaction mixture. Full CO conversion was obtained after the light-off temperature in the case of the modified cell, contrary to the case of the original cell, for which 80% of the reaction mixture bypassed the catalyst bed. The water-gas shift reaction over a Pt/CeO2 catalyst was used as a model reaction to further characterize the behavior of the cell under reaction conditions. The catalyst bed was shown not to be a dead-zone and was purged in essentially the same time as that needed to purge the cell. The reaction chamber globally operated in a quasi plug-flow mode and the gas composition in the thin catalyst bed appears to be homogeneous when operated under differential conditions. The production of the gas-phase reaction product CO2 could be simultaneously followed both by mass spectrometry and DRIFTS, both techniques leading to identical results. Various IR bands integration methods were discussed to allow a precise and accurate determination of the surface concentration of adsorbates during isotopic exchange. (c) 2008 Elsevier B.V. All rights reserved.

A kinetic study of ammonia oxidation on a Pt catalyst in the explosive region in a microstructured reactor/heat-exchanger

The application of an aluminum-based microstructured reactor/heat-exchanger for measuring reaction kinetics in the explosive region is presented. Platinum-catalyzed ammonia oxidation was chosen as a test reaction to demonstrate the feasibility of the method. The reaction kinetics was investigated in a wide range of conditions [NH3 partial pressure: 0.03-0.20 atm, O-2 partial pressure: 0.10-0.88atm; reactant flow 2000-3000 cm(3) min(-1) (STP); temperature 240-360degreesC] over a supported Pt/Al2O3 catalyst (mass of Al2O3 layer in the reactor, 1.95 mg; Pt/Al molar ratio, 0.71; Pt dispersion, 20%). The maximum temperature non-uniformity in the microstructured reactor was ca. 5degreesC, even at conditions corresponding to an adiabatic temperature rise of 1400degreesC. Based on the data obtained, a previous kinetic model for ammonia oxidation was extended. The modified 13-step model describes the data in a considerably wider range of conditions including those with high ammonia loadings and high reaction temperatures. The results indicate the large potential of microstructured devices as reliable tools for kinetic research of highly exothermic reactions.

Benzimidazole carbamate residues in milk: Detection by Surface Plasmon Resonance-biosensor, using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method for extraction

A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5(6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjugate. A sample preparation procedure was developed using a modified QuEChERS method. BZT residues were extracted from milk using liquid extraction/partition with a dispersive solid phase extraction clean-up step. The assay was validated in accordance with the performance criteria described in 2002/657/EC. The limit of detection of the assay was calculated from the analysis of 20 known negative milk samples to be 2.7 mu g kg(-1). The detection capability (CC beta) of the assay was determined to be 5 mu g kg(-1) for 11 benzimidazole residues and the mean recovery of analytes was in the range 81-116%. A comparison was made between the SPR-biosensor and UPLC-MS/MS analyses of milk samples (n = 26) taken from cows treated different benzimidazole products, demonstrating the SPR-biosensor assay to be fit for purpose. (C) 2009 Elsevier B.V. All rights reserved.

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.

Enhancing the Activity and Tuning the Mechanism of Formic acid Oxidation at Tetrahexahedral Pt Nanocrystals by Au Decoration

Tetrahexahedral Pt nanocrystals (THH Pt NCs), bound by high index facets, belong to an emerging class of nanomaterials that promise to bridge the gap between model and practical electrocatalysts. The atomically stepped surfaces of THH Pt NCs are extremely active for the electrooxidation of small organic molecules but they also readily accommodate the dissociative chemisorption of such species, resulting in poisoning by strongly adsorbed CO. Formic acid oxidation is an ideal reaction for studying the balance between these competing catalyst characteristics, since it can proceed by either a direct or a CO mediated pathway. Herein, we describe electrochemical and in situ FTIR spectroscopic investigations of formic acid electrooxidation at both clean and Au adatom modified THH Pt NC surfaces. The Au decoration leads to higher catalytic currents and enhanced CO2 production in the low potential range. As the CO oxidation behaviour of the catalyst is not changed by the presence of the Au, it is likely that the role of the Au is to promote the direct pathway. Beyond their fundamental importance, these results are significant in the development of stable, poison resistant anodic electrocatalysts for direct formic acid fuel cells.

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

Identification of CO adsorbed at Ru and Pt sites on a polycrystalline Pt/Ru electrode and the observation of their oxidation and free interchange under open circuit conditions

The spontaneous oxidation of CO adsorbates on a Pt electrode modified by Ru under open circuit (OC) conditions in perchloric acid solution has been followed, for the first time, using in situ FTIR spectroscopy, and the dynamics of the surface processes taking place have been elucidated. The IR data show that adsorbed CO present on both the Ru and Pt domains and can be oxidized by the oxygen-containing adlayer on the Ru in a chemical process to produce CO under OC conditions. There is a free exchange of CO is between the Ru and Pt sites. Oxidation of CO may take place at the edges of the Ru islands, but CO is transfer, at least on the time scale of these experiments, allows the two different populations to maintain equilibrium. Oxidation is limited in this region by the rate of supply of oxygen to die surface of the catalyst. A mechanism is postulated to explain the observed behavior.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.