Full-Space Electric Field in Mo-Decorated Zn 2 In 2 S 5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production.

Integration of photocatalytic hydrogen (H 2 ) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H 2 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, we overcome this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated Zn 2 In 2 S 5 (Mo-Zn 2 In 2 S 5 ) 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 Zn 2 In 2 S 5 . Notably, the optimized Mo 1.5 -Zn 2 In 2 S 5 catalyst achieves exceptional H 2 and benzaldehyde production rates of 34.35 and 45.31 mmol g cat -1 h -1 , respectively, outperforming pristine ZnIn 2 S 4 by 3.83- and 4.15-fold. Our findings mark a significant stride in steering charge flow for enhanced photocatalytic performance. This article is protected by copyright. All rights reserved.