Exploring durable electrocatalysts with high activity for oxygen evolution reaction (OER) in acidic media is of paramount importance for H2 production via polymer electrolyte membrane electrolyzers, yet it remains urgently challenging. Herein, we report a synergistic strategy of Rh doping and surface oxygen vacancies to precisely regulate unconventional OER reaction path via the Ru-O-Rh active sites of Rh-RuO2, simultaneously boosting intrinsic activity and stability. The stabilized low-valent catalyst exhibits a remarkable performance, with an overpotential of 161 mV at 10 mA cm-2 and activity retention of 99.2% exceeding 700 h at 50 mA cm-2. Quasi in situ/operando characterizations demonstrate the recurrence of reversible oxygen species under working potentials for enhanced activity and durability. It is theoretically revealed that Rh-RuO2 passes through a more optimal reaction path of lattice oxygen mediated mechanism-oxygen vacancy site mechanism induced by the synergistic interaction of defects and Ru-O-Rh active sites with the rate-determining step of *O formation, breaking the barrier limitation (*OOH) of the traditional adsorption evolution mechanism.
© 2023. The Author(s).