Large electronegativity differences between adjacent atomic sites activate and stabilize ZnIn₂S₄ for efficient photocatalytic overall water splitting

Photocatalytic overall water splitting into hydrogen and oxygen is desirable for long-term renewable, sustainable and clean fuel production on earth. Metal sulfides are considered as ideal hydrogen-evolved photocatalysts, but their component homogeneity and typical sulfur instability cause an inert oxygen production, which remains a huge obstacle to overall water-splitting. Here, a distortion-evoked cation-site oxygen doping of ZnIn₂S₄ (D-O-ZIS) creates significant electronegativity differences between adjacent atomic sites, with S₁ sites being electron-rich and S₂ sites being electron-deficient in the local structure of S₁–S₂–O sites. The strong charge redistribution character activates stable oxygen reactions at S₂ sites and avoids the common issue of sulfur instability in metal sulfide photocatalysis, while S₁ sites favor the adsorption/desorption of hydrogen. Consequently, an overall water-splitting reaction has been realized in D-O-ZIS with a remarkable solar-to-hydrogen conversion efficiency of 0.57%, accompanying a ~ 91% retention rate after 120 h photocatalytic test. In this work, we inspire an universal design from electronegativity differences perspective to activate and stabilize metal sulfide photocatalysts for efficient overall water-splitting.