![]() As a key half-reaction, OER needs higher energy to overcome the kinetic barrier due to the four-electron transfer reaction 5, 6, 7. Oxygen evolution reaction (OER) plays an undoubtedly vital role in the energy conversion system, which involves hydrogen production through water electrolysis, CO 2 reduction to generate clean small molecule fuel, and the application of energy conversion devices such as metal-air batteries 1, 2, 3, 4. It is theoretically revealed that Rh-RuO 2 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. Quasi in situ/operando characterizations demonstrate the recurrence of reversible oxygen species under working potentials for enhanced activity and durability. 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. 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-RuO 2, simultaneously boosting intrinsic activity and stability. Exploring durable electrocatalysts with high activity for oxygen evolution reaction (OER) in acidic media is of paramount importance for H 2 production via polymer electrolyte membrane electrolyzers, yet it remains urgently challenging.
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