Co-Co Dinuclear Active Sites Dispersed on Zirconium-doped Heterostructured Co₉ S₈ /Co₃ O₄ for High-current-density and Durable Acidic Oxygen Evolution

Developing cost-effective and sustainable acidic water oxidation catalysts requires significant advances in material design and in-depth mechanism understanding for proton exchange membrane water electrolysis. Herein, we developed a single atom regulatory strategy to construct Co-Co dinuclear active sites (DASs) catalysts that atomically dispersed zirconium doped Co₉ S₈ /Co₃ O₄ heterostructure. The X-ray absorption fine structure elucidated the incorporation of Zr greatly facilitated the generation of Co-Co DASs layer with stretching of cobalt oxygen bond and S-Co-O heterogeneous grain boundaries interfaces, engineering attractive activity of significantly reduced overpotential of 75 mV at 10 mA cm^-2 , a breakthrough of 500 mA cm^-2 high current density, and water splitting stability of 500 hours in acid, making it one of the best-performing acid-stable OER non-noble metal materials. The optimized catalyst with interatomic Co-Co distance (ca. 2.80 Å) followed oxo-oxo coupling mechanism that involved obvious oxygen bridges on dinuclear Co sites (1,090 cm^-1 ), confirmed by in situ SR-FTIR, XAFS and theoretical simulations. Furthermore, a major breakthrough of 120,000 mA g^-1 high mass current density using the first reported noble metal-free cobalt anode catalyst of Co-Co DASs/ZCC in PEM-WE at 2.14 V was recorded.