Cation/Anion Dual-Vacancy Pair Modulated Atomically-Thin Se_x -Co₃ S₄ Nanosheets with Extremely High Water Oxidation...

The density functional theory calculation results reveal that the adjacent defect concentration and electronic spin state can effectively activate the Co^III sites in the atomically thin nanosheets, facilitating the thermodynamic transformation of *O to *OOH, thus offering ultrahigh charge transfer properties and efficiently stabilizing the phase. This undoubtedly evidences that, for metal sulfides, the atom-scale cation/anion vacancy pair and surface electronic spin state can play a great role in enhancing the oxygen evolution reaction. Inspired by the theoretical prediction, interconnected selenium (Se) wired ultrathin Co₃ S₄ (Se_x -Co₃ S₄ ) nanosheets with Co/S (Se) dual-vacancies (Se_1.0 -Co₃ S₄ -V_S/Se -V_Co ) pairs are constructed by a simple approach. As an efficient sulfur host material, in an ultralow-concentration KOH solution (0.1 m), Se_1.0 -Co₃ S₄ -V_S/Se -V_Co presents outstanding durability up to 165 h and a low overpotential of 289.5 mV at 10 mA cm^-2 , which outperform the commercial Co₃ S₄ nanosheets (NSs) and RuO₂ . Moreover, the turnover frequency of Se_1.0 -Co₃ S₄ -V_S/Se -V_Co is 0.00965 s^-1 at an overpotential of 0.39 V, which is 5.7 times that of Co₃ S₄ NSs, and 5.8 times that of commercial RuO₂ . The finding offers a rational design strategy to create the multi-defect structure in catalysts toward high-efficiency water electrolysis.