Architecting Dynamic Oxygen Migration Pathways for Stabilizing Ru─O Sites During Acidic Electrochemical Oxidation

Abstract Ruthenium (Ru)‐based catalysts hold great promise for acidic oxidation reactions but suffer from rapid deactivation due to over‐oxidation‐induced dissolution. Herein, a dynamic support repair strategy is proposed that stabilizes Ru─O sites by architecting oxygen migration pathways during electrochemical process. In this design, screened oxygen‐deficient manganese dioxide (MnO x ) serves as a dynamic oxygen buffer that not only accepts excessive oxygen from the electrochemical oxidation of Ru─O sites, but also undergoes rapid hydroxyl‐mediated chemical reduction to transfer oxygen away and regenerate oxygen vacancies, thereby establishing a dynamic migration pathway coupling electrochemical oxidation with chemical reduction. This system delivers exceptional stability, enabling 1,000 h of oxidation reaction without potential decay‒a 40‐fold improvement compared to RuO 2 without support. Stability mechanistic analysis reveals a vacancy‐guided oxygen migration pathway that prevent over‐oxidation of Ru─O sites by transiently transferring excessive oxygen. These findings redefine the stabilization strategy for Ru‐based oxidation catalysts under harsh electrochemical environments.