Theory and modeling of catalytic and electrocatalytic reactions

Abstract

A review of the main theor. principles and computer modeling techniques to describe catalytic and electrocatalytic reactions is presented. Our guiding principles in understanding the relationship between electronic structure and catalyst performance are the periodic table and the Sabatier principle. We discuss the different modeling tactics in describing quantum-mech. adsorbate-surface interactions (i.e., cluster vs. slab models) and their accuracy in modeling (small) catalyst particles. The role of the solvent in electrocatalytic processes is described both from the point of view of quantum-chem. d.-functional theory calcns., and from more classical Marcus theory-type considerations using mol. dynamics simulations. Furthermore, we discuss how kinetic Monte Carlo methods can be used to bridge the gap between microscopic reaction models and the catalyst's macroscopic performance in an accurate statistical and mech. way. [on SciFinder (R)]