Elucidating Electrocatalytic Oxygen Reduction Kinetics via Intermediates by Time‐Dependent Electrochemiluminescence

Abstract

AbstractFacile evaluation of oxygen reduction reaction (ORR) kinetics for electrocatalysts is critical for sustainable fuel‐cell development and industrial H2O2 production. Despite great success in ORR studies using mainstream strategies, such as the membrane electrode assembly, rotation electrodes, and advanced surface‐sensitive spectroscopy, the time and spatial distribution of reactive oxygen species (ROS) intermediates in the diffusion layer remain unknown. Using time‐dependent electrochemiluminescence (Td‐ECL), we report an intermediate‐oriented method for ORR kinetics analysis. Owing to multiple ultrasensitive stoichiometric reactions between ROS and the ECL emitter, except for electron transfer numbers and rate constants, the potential‐dependent time and spatial distribution of ROS were successfully obtained for the first time. Such exclusively uncovered information would guide the development of electrocatalysts for fuel cells and H2O2 production with maximized activity and durability.