RECENT ADVANCES IN THEORETICAL ASPECTS OF ELECTROCATALYSIS

ELIZABETH SANTOS AND WOLFGANG SCHMICKLER

Modern Aspects of the Electrochemistry, Number 46: “Advances in Electrocatalysis".

Edited by Ralph E. White, Perla Balbuena, Venkat Subramanian. Springer Verlag.

Año: 2009;

In our group we have developed a new approach for electrochemical system, using DFTcalculations as input in the SKS Hamiltonian developed by Santos, Koper and Schmickler15,16.In the framework of this model electronic interactions with the electrode and with the solventcan be included in a natural way. Before giving the details of this theory, we review thedifferent phenomena involved in electrochemical reactions in order to understand themechanism of electrocatalysis and the differences with catalysis in surface science. Next, abrief summary of previous models will be given, and finally the SKS Hamiltonian model willbe discussed. We will show how the different particular approaches can be obtained on thebasis of the generalized model. As a first step, idealized semielliptical bands shapes will beconsidered in order to understand the effect of different parameters on the electrocatalyticproperties. Then, real systems will be characterized by means of DFT (Density FunctionalTheory). These calculations will be inserted as input in the SKS Hamiltonian. Applications tocases of practical interest will be examined including the effect not only of the nature of thematerial but also structural aspects, especially the electrocatalysis with differentnanostructures.