Dual‐Vacancy‐Engineered ZnIn2S4 Nanosheets for Harnessing Low‐Frequency Vibration Induced Piezoelectric Polarization Coupled with Static Dipole Field to Enhance Photocatalytic H2 Evolution

Abstract This study investigates the impact of In‐ and S‐vacancy concentrations on the photocatalytic activity of non‐centrosymmetric zinc indium sulfide (ZIS) nanosheets for the hydrogen evolution reaction (HER). A positive correlation between the concentrations of dual In and S vacancies and the photocatalytic HER rate over ZIS nanosheets is observed. The piezoelectric polarization, stimulated by low‐frequency vortex vibration to ensure the well‐dispersion of ZIS nanosheets in solution, plays a crucial role in enhancing photocatalytic HER over the dual‐vacancy engineered ZIS nanosheets. The piezoelectric characteristic of the defective ZIS nanosheets is confirmed through the piezopotential response measured using piezoelectric force microscopy. Piezophotocatalytic H 2 evolution over the ZIS nanosheets is boosted under accelerated vortex vibrations. The research explores how vacancies alter ZIS's dipole moment and piezoelectric properties, thereby increasing electric potential gradient and improving charge‐separation efficiency, through multi‐scale simulations, including Density Functional Theory and Finite Element Analysis, and a machine‐learning interatomic potential for defect identification. Increased In and S vacancies lead to higher electric potential gradients in ZIS along 100 and 010 directions, attributing to dipole moment and the piezoelectric effect. This research provides a comprehensive exploration of vacancy engineering in ZIS nanosheets, leveraging the piezopotential and dipole field to enhance photocatalytic performances.