Proceedings of nanoGe September Meeting 2015 (NFM15)
Publication date: 8th June 2015
This talk will outline a simple but general theoretical analysis for multiple proton-electron transfer reactions, based on the microscopic theory of proton-coupled electron transfer reactions, recent developments in the thermodynamic theory of multi-step electron transfer reactions, and the experimental realization that many multiple proton-coupled electron transfer reactions feature decoupled proton-electron steps in their mechanism. The theory highlights the importance of solvent reorganization as included in the Marcus theory, the energetics of intermediates as in the theory of catalytic processes, and the role of pH in optimizing acid-base reactions involved in the overall mechanism of the catalytic reaction. The theory will be discussed in relation to the experimental results for a number of redox reactions that are of importance for sustainable energy conversion, including hydrogen en oxygen evolution, and the electrocatalytic reduction of CO2, focusing on the stabilization of the catalytic intermediates, the pH dependence of the individual reaction steps, and the sensitivity of bond-breaking or bond-making steps to the structure of the heterogeneous catalyst.