Elementary Steps of the Oxygen Reduction Reaction on Nitrogen‐Doped Graphene Revealed by Raman Spectroelectrochemistry

Abstract Nitrogen‐doped graphene (N‐doped graphene) is a promising material for electrochemical applications, particularly as a catalyst in the oxygen reduction reaction (ORR). Despite numerous studies, the detailed mechanism of ORR on N‐doped graphene remains unresolved. This study utilizes spectroelectrochemical Raman (SEC‐Raman) spectroscopy to investigate the elementary steps of the ORR on graphene doped with pyridinic and graphitic nitrogen configurations. A comprehensive Raman spectral analysis reveals the evolution of adsorbed species and active sites during the reaction, suggesting an unconventional pathway involving outer‐sphere electron transfer and unique adsorption dynamics. These insights clarify the interplay between nitrogen configurations and catalytic performance, offering a deeper understanding of the structure‐activity relationship in N‐doped graphene. The findings pave the way for improved design and optimization of metal‐free ORR electrocatalysts.