Abstract
This paper offers a perspective on inner-sphere heterogeneous electron-transfer reactions and electrocatalysis as it is applied to electrochemical energy conversion systems. Fundamental concepts and an overview of past approaches to studies of these types of reactions are discussed. A method for the discovery of new electrocatalysts (for example, ones for the oxygen reduction reaction) and photocatalysts (for solar energy conversion to fuels) based on scanning electrochemical microscopy is briefly described, as well as new surface interrogation techniques for quantifying intermediates.