Unraveling the Asymmetric O─O Radical Coupling Mechanism on Ru─O─Co for Enhanced Acidic Water Oxidation

Heterogeneous oxides with multiple interfaces provide significant advantages in electrocatalytic activity and stability. However, controlling the local structure of these oxides is challenging. In this work, unique heterojunctions are demonstrated based on two oxide types, which are formed via pyrolysis of a ruthenocene metal-organic framework (Ru-MOF) at specific temperatures. The resulted Ru-MOF-400 exhibits excellent electrocatalytic activity, with an overpotential of 190 mV at a current density of 10 mA cm^-2 in 0.1 m HClO₄ , and a mass activity of 2557 A g_Ru ^-1 , three orders of magnitude higher than commercial RuO₂ . The Ru─O─Co bond formed by the incorporation of Co into the rutile lattice of RuO₂ inhibits the disolution of Ru. Operando electrochemical investigations and density functional theory results reveal that the Ru-MOF-400 undergo asymmetric dual-active site oxide path mechanism during the acidic oxygen evolution reaction process, which is predominantly mediated by the asymmetric Ru─Co dual active site present at the interfaces between Co₃ O₄ and CoRuO_x .