Electrode Potential Dependence of Elementary Reaction Steps in Electrocatalysis: Development of Ab Initio Methodology and Applications

Case Western Reserve University, Cleveland OH

Investigators

Abstract

Calculational studies of the elementary steps of electrocatalysis form the focus of this research project supported in the Analytical and Surface Chemistry Program. Professor Alfred B. Anderson's research group at Case Western applies ab initio quantum mechanical calculations to the study of electron and proton transfer at the electrochemical interface. Density functional correlation corrected methods are used to examine the four electron reduction of oxygen to water and the oxidation of CO by water and hydroxyl at the platinum electrode surface. The electrode potential dependence of the fundamental reaction steps is emphasized, and comparisons with experimental studies carried out by collaborators at Case Western are included. In order to understand the detailed microscopic mechanism of electrode reactions important to electrocatalysis and fuel cell design, quantum chemical calculations are used to determine the kinetic and energetic pathways for molecular processes on the electrode surface. This project, supported by the Analytical and Surface Chemistry Program, addresses these questions of microscopic reaction mechanism. Professor Anderson's group at Case Western examines the reduction of oxygen and the oxidation of CO as important model systems for these electrocatalytic processes. Information from these studies will be useful in the design and engineering of fuel cell and electrocatalytic systems.