Pressure‐Assisted Ni 3d–S 3p Hybridization within Targeted In–S Layer for Enhanced Photocatalytic Hydrogen Production

Abstract Solar‐driven hydrogen production is significant for achieving carbon neutrality but is limited by unsatisfactory surface catalytic reaction kinetics. Layer regulation can impact carrier transmission or catalytic behavior, but the specific effects on the oxygen or hydrogen evolution reaction (OER or HER) remain unclear, and atomic layer level modulation for maxing HER is challenging. Here the distinct roles of modulated Zn–S or In–S surface layers in ZnIn₂S₄ (ZIS) for the OER and HER, respectively, are disentangled. Moreover, the 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, ≈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.