Charge redistribution within surface In–S layer of ZnIn2S4 for enhanced visible light-driven hydrogen evolution

Solar-driven hydrogen production is significative for achieving carbon neutrality while is limited by inefficient photocatalysts. Atomic layer regulation can impact carrier transmission or catalytic behavior for active photocatalyst design, but the specific effects on the oxygen or hydrogen evolution reaction (OER or HER) remain unclear, and precise atomic layer level regulation is challenging. Here we disentangle the distinct roles of modulated Zn–S or In–S surface layers in ZnIn2S4 (ZIS) for the OER and HER, respectively. Moreover, our extensive characterizations and computational results demonstrate that stressful environments enable individual modulation and introduce Ni into the surface In–S layer rather than the easily alterable Zn–S layer, creating deeper hybridized electronic states of Ni 3d-S 3p, optimizing H* adsorption/desorption, and maximizing surface catalytic benefits for the HER. Consequently, the optimized ZIS exhibited a photocatalytic hydrogen production rate of up to 18.19 mmol g-1 h-1, approximately 32 times higher than pristine ZIS. This investigation expands the application scenarios of ultrasonic technology and inspires other precise control types, such as defects and crystal plane engineering, etc