Advances in Oxygen Evolution Reaction Electrocatalysts via Direct Oxygen–Oxygen Radical Coupling Pathway

Abstract Oxygen evolution reaction (OER) is a cornerstone of various electrochemical energy conversion and storage systems, including water splitting, CO 2 /N 2 reduction, reversible fuel cells, and rechargeable metal‐air batteries. OER typically proceeds through three primary mechanisms: adsorbate evolution mechanism (AEM), lattice oxygen oxidation mechanism (LOM), and oxide path mechanism (OPM). Unlike AEM and LOM, the OPM proceeds via direct oxygen–oxygen radical coupling that can bypass linear scaling relationships of reaction intermediates in AEM and avoid catalyst structural collapse in LOM, thereby enabling enhanced catalytic activity and stability. Despite its unique advantage, electrocatalysts that can drive OER via OPM remain nascent and are increasingly recognized as critical. This review discusses recent advances in OPM‐based OER electrocatalysts. It starts by analyzing three reaction mechanisms that guide the design of electrocatalysts. Then, several types of novel materials, including atomic ensembles, metal oxides, perovskite oxides, and molecular complexes, are highlighted. Afterward, operando characterization techniques used to monitor the dynamic evolution of active sites and reaction intermediates are examined. The review concludes by discussing several research directions to advance OPM‐based OER electrocatalysts toward practical applications.