Atomically Dispersed Vanadium-Induced Ru-V Dual Active Sites Enable Exceptional Performance for Acidic Water Oxidation

Regulating the catalytic reaction pathway to essentially break the activity/stability trade-off that limits RuO₂ and thus achieves exceptional stability and activity for the acidic oxygen evolution reaction (OER) is important yet challenging. Herein, we propose a novel strategy of incorporating atomically dispersed V species, including O-bridged V dimers and V single atoms, into RuO₂ lattices to trigger direct O−O radical coupling to release O₂ without the generation of *OOH intermediates. V_n−RuO₂ showed high activity with a low overpotential of 227 mV at 10 mA cm⁻² and outstanding stability during a 1050 h test in acidic electrolyte. Operando spectroscopic studies and theoretical calculations revealed that compared with the V single atom-doping case, the introduction of the V dimer into RuO₂ further decreases the Ru-V atomic distance and weakens the adsorption strength of the *O intermediate to the active V site, which supports the more energetically favorable oxygen radical coupling mechanism (OCM). Furthermore, the highly asymmetric Ru−O−V local structure stabilizes the surface Ru active center by lowering the valence state and increasing the resistance against overoxidation, which result in outstanding stability. This study provides insight into ways of increasing the intrinsic catalytic activity and stability of RuO₂ by atomically dispersed species modification. © 2024 Wiley-VCH GmbH.