Kinetics of cluster shape sensitive heterogeneous catalytic reactions

The theoretical framework for analysis of heterogeneous catalytic reactions on metals clusters sensitive to the cluster shape has been developed. Cubooctahedrons, cubes and semi-spherical particles have been considered having a different number of edge, corner, terrace and perimeter sites. A general expression of size/shape dependent kinetics is derived for multi-step reactions relating the Gibbs energy for elementary steps, comprising the reaction network, with the Gibbs energy of adsorbed intermediates on different sites. A comparison of the turnover frequency for catalytic reactions on cuboctahedrons and cubes of the same size is provided for a two-step sequence and a Langmuir-Hinshelwood mechanism.