Surface studies of supported model catalysts

Palladium-based catalysts are widely applied in exhaust catalytic converter and catalytic combustion systems. The mechanism for methane oxidation on a Pd-based catalyst is complex. Catalyst activity is influenced by variations in the process pressure and temperature, by the gas mixture composition, by the type of support and various additives, and by pretreatment under reducing or oxidizing atmospheres. In this paper, we review the literature on supported Pd catalysts for combustion of methane. The mechanisms involved are discussed taking into consideration the oxidation/reduction mechanisms for supported palladium, poisoning, restructuring, the form of oxygen on the surface, methane activation over Pd and PdO phases, and transient behavior. Our review helps explain the array of experimental results reported in the literature.

Catalytic combustion of methane over palladium-based catalysts

Nanoscale structural information underlies research aimed at fabricating catalysts in a more controlled way. Surface science methods can provide that information, but the complexity of heterogeneous systems in general hinders the application of these methods to their full potential. In the last decades, a solution to this problem has been found in the use of model systems, ranging from well-defined single crystals of the supported phase to films or particles of that phase on flat or spherical model supports. In this paper, we review the literature on the latter model systems, that is, particles on a model support. Attention is payed to both preparation and use of such model systems.

https://pure.tue.nl/ws/files/1495087/617871.pdf

Surface Science Approach to Modeling Supported Catalysts

A theory is developed which allows one to discuss the stability of multiply-twinned particles and to calculate critical sizes for stable and quasi-stable states. An icosahedral particle is essentially stable for r ≦ r i w * , quasi-stable for r i w * r i t 0 where r is an edge length of the particle, while a decahedral particle is not essentially stable but quasi-stable for r ≦ r d t 0 and unstable for r > r d t 0 . The critical sizes r i w * , r i t 0 and r d t 0 are formulated as functions of the specific surface energy γ h k l , the twin boundary energy γ t , the elastic strain energy W and the adhesive energy γ a to the substrate. Calculated critical diameters 2 r i w * ,2 r i t 0 and 2 r d t 0 for the particles grown in free space for several elements range between 15.5A and 106.8A, between 109.8A and 486.1A and between 725A and 3961A, respectively. These values are in good agreement with experimental results.

Stability of Multiply-Twinned Particles

The diesel oxidation catalyst (DOC) has been part of diesel exhaust systems since regulations were introduced to limit the amount of harmful emissions released to the environment from diesel engines. The DOC primary functions are oxidation of CO, unburned hydrocarbons, and NO, while active hydrocarbon oxidation can also be used to generate exotherms required for downstream components. This review will describe work that has attempted to understand the reactions, both desired and undesired, that occur over the catalyst. First, the history, configuration, and components of the DOC will be discussed, followed by in-depth coverage of the fundamental reactions that occur over a DOC, including reaction mechanisms, reaction inhibition, and other reactivity effects. Finally, DOC deactivation mechanisms and their effects on the DOC are described. While there is a lot of research literature regarding Pt- and Pd-based catalysts for many different reaction schemes, this review tries to highlight work most relevant to...

M. Chen

Papers

Morphology and composition of PtPd alloy crystallites on SiO2 in reactive atmospheres

Morphology and sintering of Pt crystallites on amorphous SiO2

Morphology of Pt-Rh alloy crystallites on amorphous SiO2*1