Heterogeneous catalysis deactivation

Zeolites have led to a new phenomenon in heterogeneous catalysis, shape selectivity. It has two aspects (a) formation of an otherwise possible product is blocked because it cannot fit into the pores, and (b) formation of the product is blocked not by (a) but because the transition state in the bimolecular process leading to it cannot fit into the pores. For example, (a) is involved in zeolite catalyzed reactions which favor a para-disubstituted benzene over the ortho and meso. The low rate of deactivation observed in some reactions of hydrocarbons on some zeoUtes has been ascribed to (b) inhibition of bimolecular steps forming coke. 

Measurement of heat of adsorption by means of microcalorimetry has been used extensively in heterogeneous catalysis to gain more insight into the strength of gas-surface interactions and the catalytic properties of solid surfaces [61-65]. Microcalorimetry coupled with volumetry is undoubtedly the most reliable method, for two main reasons (i) the expected physical quantities (the heat evolved and the amount of adsorbed substance) are directly measured (ii) no hypotheses on the actual equilibrium of the system are needed. Moreover, besides the provided heat effects, adsorption microcalorimetry can contribute in the study of all phenomena, which can be involved in one catalyzed process (activation/deactivation of the catalyst, coke production, pore blocking, sintering, and adsorption of poisons in the feed gases) [66]. 

The catalyst turnover number (TON) and the turnover frequency (TOF) are two important quantities used for comparing catalyst efficiency. Their definitions, however, vary slightly among the three catalysis fields. In homogeneous catalysis, the TON is the number of cycles that a catalyst can run through before it deactivates, i.e., the number of A molecules that one molecule of catalyst can convert (or turn over ) into B molecules. The TOF is simply TON/time, i.e., the number of A molecules that one molecule of catalyst can convert into B molecules in one second, minute, or hour. In heterogeneous catalysis, TON and TOF are often defined per active site, or per gram catalyst. This is because one does not know exactly how many... 

Heterogeneous catalysis is a surface phenomenon, therefore the overall kinetic parameters are dependent on the real exposed catalyst surface area. In the supported systems only a part of the photocatalyst is accessible to light and to substrate. Besides, the immobilized catalyst suffers from the surface deactivation since the support could enhance the recombination of photogenerated electron-hole pairs and a limitation of oxygen diffusion in the deeper layers is observed. 

Moulijn JA, van Diepen AE, Kapteijn F. Deactivation and regeneration. In Ertl G, Knozinger H, Weitkamp J, editors. Handbook of heterogeneous catalysis. 2nd ed. Weinheim Wiley-VCH Verlag GmbH Co. KGaA 2008. p. 1-18. 

The use of transmission electron microscopy in heterogeneous catalysis centers around particle size distribution measurement, particle morphology and structural changes in the support. Consideration is given to the limitations of conventional electron microscopy and how modifications to the instrument enable one to conduct in-situ experiments and be in a position to directly observe many of the features of a catalyst as it participates in a reaction. In order to demonstrate the power of the in-situ electron microscopy technique examples are drawn from areas which impact on aspects of catalyst deactivation. In most cases this information could not have been readily obtained by any other means. Included in this paper is a synopsis of the methods available for preparing specimens of model and real catalyst systems which are suitable for examination by transmission electron microscopy. 

The deposition of tungsten by CVD is essentially a catalytic heterogeneous reaction. The tungsten surface acts as the catalyst to activate either the H2 or the SiH4 molecules depending on what chemistry is in use. It is well known from heterogeneous catalysis that extremely low concentrations of surface active contaminants can deactivate the surface and block or slow down the reaction rate. However, it is also possible that certain active molecules can accelerate the deposition once they become adsorbed to the tungsten surface. 

J.W. Lee, J.B. Butt and D.M. Downing, Kinetic, transport, and deactivation rate interactions on steady state and transient response in heterogeneous catalysis, A.I.Ch.E.J. 24(1978)212. 

Conventional heterogeneous catalysis and empiricism could provide a starting point in the selection of electrocatalysts for new unexplored processes for chemical production, energy generation or conservation, and environmental control. However, a fundamental understanding of adsorption characteristics, electrode kinetics, mechanisms, adsorbate-support interactions, and deactivation processes are needed for improved electrocatalyst... 

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