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Microkinetic Analysis and Scaling Relations for Catalyst Design.

Microkinetic analysis plays an important role in catalyst design because it provides insight into the fundamental surface chemistry that controls catalyst performance. In this review, we summarize the development of microkinetic models and the inclusion of scaling relationships in these models. We discuss the importance of achieving stoichiometric and thermodynamic consistency in developing microkinetic models. We also outline how analysis of the maximum rates of elementary steps can be used to determine which transition states and adsorbed intermediates are kinetically significant, allowing the derivation of general reaction kinetics rate expressions in terms of changes in binding energies of the relevant transition states and intermediates. Through these analyses, we present how to predict optimal surface coverages and binding energies of adsorbed species, as well as the extent of potential rate improvement for a catalytic system. For systems in which the extent of potential rate improvement is small because of limitations imposed by scaling relations, different approaches, including the addition of promoters and formation of catalysts containing multiple functionalities, can be used to break the scaling relations and obtain further rate enhancement.

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