DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

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.

On the complexity of the water-gas shift reaction mechanism over a Pt/CeO2 catalyst: Effect of the temperature on the reactivity of formate surface species studied by operando DRIFT during isotopic transient at chemical steady-state

The present report investigates the role of formate species as potential reaction intermediates for the WGS reaction (CO + H2O -> CO2 + H-2) over a Pt-CeO2 catalyst. A combination of operando techniques, i.e., in situ diffuse reflectance FT-IR (DRIFT) spectroscopy and mass spectrometry (MS) during steady-state isotopic transient kinetic analysis (SSITKA), was used to relate the exchange of the reaction product CO2 to that of surface formate species. The data presented here suggest that a switchover from a non-formate to a formate-based mechanism could take place over a very narrow temperature range (as low as 60 K) over our Pt-CeO2 catalyst. This observation clearly stresses the need to avoid extrapolating conclusions to the case of results obtained under even slightly different experimental conditions. The occurrence of a low-temperature mechanism, possibly redox or Mars van Krevelen-like, that deactivates above 473 K because of ceria over-reduction is suggested as a possible explanation for the switchover, similarly to the case of the CO-NO reaction over Cu, I'd and Rh-CeZrOx (see Kaspar and co-workers [1-3]). (c) 2006 Elsevier B.V. All rights reserved.

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.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

Pulse-response TAP studies of the reverse water-gas shift reaction over a Pt/CeO2 catalyst

The temporal analysis of products (TAP) technique was successfully applied for the first time to investigate the reverse water-gas shift (RWGS) reaction over a 2% Pt/CeO2 catalyst. The adsorption/desorption rate constants for CO2 and H-2 were determined in separate TAP pulse-response experiments, and the number of H-containing exchangeable species was determined using D-2 multipulse TAP experiments. This number is similar to the amount of active sites observed in previous SSITKA experiments. The CO production in the RWGS reaction was studied in a TAP experiment using separate (sequential) and simultaneous pulsing Of CO2 and H-2. A small yield of CO was observed when CO2 was pulsed alone over the reduced catalyst, whereas a much higher CO yield was observed when CO2 and H-2 were pulsed consecutively. The maximum CO yield was observed when the CO2 pulse was followed by a H-2 pulse with only a short (1 s) delay. Based on these findings, we conclude that an associative reaction mechanism dominates the RWGS reaction under these experimental conditions. The rate constants for several elementary steps can be determined from the TAP data. In addition, using a difference in the time scale of the separate reaction steps identified in the TAP experiments, it is possible to distinguish a number of possible reaction pathways. (c) 2005 Elsevier Inc. All rights reserved.

The Development of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications.

This paper describes the development of a two-dimensional transient catalyst model. Although designed primarily for two-stroke direct injection engines, the model is also applicable to four-stroke lean burn and diesel applications. The first section describes the geometries, properties and chemical processes simulated by the model and discusses the limitations and assumptions applied. A review of the modeling techniques adopted by other researchers is also included. The mathematical relationships which are used to represent the system are then described, together with the finite volume method used in the computer program. The need for a two-dimensional approach is explained and the methods used to model effects such as flow and temperature distribution are presented. The problems associated with developing surface reaction rates are discussed in detail and compared with published research. Validation and calibration of the model is achieved by comparing predictions with measurements from a flow reactor. While an extensive validation process, involving detailed measurements of gas composition and thermal gradients, has been completed, the analysis is too detailed for publication here and is the subject of a separate technical paper.

The Validation of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications

This paper describes the detailed validation of a computer model designed to simulate the transient light-off in a two-stroke oxidation catalyst. A plug flow reactor is employed to provide measurements of temperature and gas concentration at various radial and axial locations inside the catalyst. These measurements are recorded at discrete intervals during a transient light-off in which the inlet temperature is increased from ambient to 300oC at rates of up to 6oC/sec. The catalyst formulation used in the flow reactor, and its associated test procedures, are then simulated by the computer and a comparison made between experimental readings and model predictions. The design of the computer model to which this validation exercise relates is described in detail in a separate technical paper. The first section of the paper investigates the warm-up characteristics of the substrate and examines the validity of the heat transfer predictions between the wall and the gas in the absence of chemical reactions. The predictions from a typical single-component CO transient light-off test are discussed in the second section and are compared with experimental data. In particular the effect of the temperature ramp on the light-off curve and reaction zone development is examined. An analysis of the C3H6 conversion is given in the third section while the final section examines the accuracy of the light-off curves which are produced when both CO and C3H6 are present in the feed gas. The analysis shows that the heat and mass transfer calculations provided reliable predictions of the warm-up behaviour and post light-off gas concentration profiles. The self-inhibition and cross-inhibition terms in the global rate expressions were also found to be reasonably reliable although the surface reaction rates required calibration with experimental data.

Simulation of the Unsteady Gas Flow through a Three-way Automotive Catalyst

This paper describes a model of a 1.8-litre four-cylinder four-stroke gasoline engine fitted with a close-coupled three-way catalyst (TWC). Designed to meet EURO 3 emissions standards, the engine includes some advanced emission control features in addition to the TWC, namely: variable valve timing (VVT), swirl control plates, and exhaust gas recirculation (EGR). Gas flow is treated as one-dimensional (1D) and unsteady in the engine ducting and in the catalyst. Reflection and transmission of pressure waves at the boundaries of the catalyst monolith are modelled. In-cylinder combustion is represented by a two-zone burn model with dissociation and reaction kinetics. A single Wiebe analysis of measured in-cylinder pressure data is used to determine the mass fraction burned as a function of crank angle (CA) at each engine speed. Measured data from steady-state dynamometer tests are presented for operation at wide open throttle (WOT) over a range of engine speeds. These results include CA-resolved traces of pressure at various locations throughout the engine together with cycle-averaged traces of gas composition entering the catalyst as indicated by a fast-response emissions analyser. Simulated engine performance and pressure wave action throughout the engine are well validated by the measured data.

An Experimental and Predictive Evaluation of Unsteady Gas Flow through Automotive Catalyst Elements

The incorporation of one-dimensional simulation codes within engine modelling applications has proved to be a useful tool in evaluating unsteady gas flow through elements in the exhaust system. This paper reports on an experimental and theoretical investigation into the behaviour of unsteady gas flow through catalyst substrate elements. A one-dimensional (1-D) catalyst model has been incorporated into a 1-D simulation code to predict this behaviour.

Experimental data was acquired using a ‘single pulse’ test rig. Substrate samples were tested under ambient conditions in order to investigate a range of regimes experienced by the catalyst during operation. This allowed reflection and transmission characteristics to be quantified in relation to both geometric and physical properties of substrate elements. Correlation between measured and predicted results is demonstrably good and the model provides an effective analysis tool for evaluating unsteady gas flow through different catalytic converter designs.