Full‐Space Electric Field in Mo‐Decorated Zn2In2S5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production

Abstract

AbstractIntegration of photocatalytic hydrogen (H2) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H2 fuel and high‐value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full‐space electric field via charge polarization engineering on a Mo cluster‐decorated Zn2In2S5 (Mo‐Zn2In2S5) photocatalyst. Specifically, this full‐space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn–S] regions to [In–S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of Zn2In2S5. Notably, the optimized Mo1.5‐Zn2In2S5 catalyst achieves exceptional H2 and benzaldehyde production rates of 34.35 and 45.31 mmol gcat−1 h−1, respectively, outperforming pristine ZnIn2S4 by 3.83‐ and 4.15‐fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.