Active Sites and Mechanisms for Oxygen Reduction Reaction on Nitrogen-Doped Carbon Alloy Catalysts: Stone–Wales Defect and Curvature Effect

Carbon alloy catalysts (CACs) are promising oxygen reduction reaction (ORR) catalysts to substitute platinum. However, despite extensive studies on CACs, the reaction sites and mechanisms for ORR are still in controversy. Herein, we present rather general consideration on possible ORR mechanisms for various structures in nitrogen doped CACs based on the first-principles calculations. Our study indicates that only a particular structure of a nitrogen pair doped Stone–Wales defect provides a good active site. The ORR activity of this structure can be tuned by the curvature around the active site, which makes its limiting potential approaching the maximum limiting potential (0.80 V) in the volcano plot for the ORR activity of CACs. The calculated results can be compared with the recent experimental ones of the half-wave potential for CAC systems that range from 0.60 to 0.80 V in the reversible-hydrogen-electrode (RHE) scale.