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.

High-performance thermogalvanic cells have the potential to convert thermal energy into electricity, but their effectiveness is limited by the low concentration difference of redox ions. We report an in situ photocatalytically enhanced redox reaction that generates hydrogen and oxygen to realize a continuous concentration gradient of redox ions in thermogalvanic devices. A linear relation between thermopower and hydrogen production rate was established as an essential design principle for devices. The system exhibited a thermopower of 8.2 millivolts per kelvin and a solar-to-hydrogen efficiency of up to 0.4%. A large-area generator (112 square centimeters) consisting of 36 units yielded an open-circuit voltage of 4.4 volts and a power of 20.1 milliwatts, as well 0.5 millimoles of hydrogen and 0.2 millimoles of oxygen after 6 hours of outdoor operation.

Severe carrier recombination and the slow kinetics of water splitting for photocatalysts hamper their efficient application. Herein, we propose a hydrovoltaic effect-enhanced photocatalytic system in which polyacrylic acid (PAA) and cobaltous oxide (CoO)–nitrogen doped carbon (NC) achieve an enhanced hydrovoltaic effect and CoO–NC acts as a photocatalyst to generate H₂ and H₂O₂ products simultaneously. In this system, called PAA/CoO–NC, the Schottky barrier height between CoO and the NC interface decreases by 33% due to the hydrovoltaic effect. Moreover, the hydrovoltaic effect induced by H⁺ carrier diffusion in the system generates a strong interaction between H⁺ ions and the reaction centers of PAA/CoO–NC, improving the kinetics of water splitting in electron transport and species reaction. PAA/CoO–NC exhibits excellent photocatalytic performance, with H₂ and H₂O₂ production rates of 48.4 and 20.4 mmol g⁻¹ h⁻¹, respectively, paving a new way for efficient photocatalyst system construction.