Abstract

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 will be discussed in relation to the experimental results for a number of redox reactions that are of importance for sustainable energy conversion, including oxygen reduction and evolution, and the electrocatalytic reduction of CO₂, focusing on their pH dependence and structure sensitivity.