Rapid Charge Transfer Endowed by Heteroatom Doped Z‐Scheme Van Der Waals Heterojunction for Boosting Photocatalytic Hydrogen Evolution

Abstract Constructing heterojunctions between phase interfaces represents a crucial strategy for achieving excellent photocatalytic performance, but the absence of sufficient interface driving force and limited charge transfer pathway leads to unsatisfactory charge separation processes. Herein, a doping‐engineering strategy is introduced to construct a In─N bond‐bridged In 2 S 3 nanocluster modified S doped carbon nitride (CN) nanosheets Z‐Scheme van der Waals (VDW) heterojunctions (In 2 S 3 /CNS) photocatalyst, and the preparation process just by one‐step pyrolysis using the pre‐coordination confinement method. Specifically, S atoms doping enhances the bond strength of In─N and forms high‐quality interfacial In─N linkage which serves as the atomic‐level interfacial “highway” for improving the interfacial electrons migration, decreasing the charge recombination probability. The detailed characterization results, along with theoretical calculations, confirm that both S atom incorporation and the formation of Z‐Scheme VDW heterojunctions synergistically improve the internal electric field. This, in turn, accelerates charge separation and simultaneously enhances light absorption capacity. Consequently, the optimal hydrogen evolution performance of In₂S₃/CNS2 is 160.8 times greater than that of In₂S₃, 8.2 times higher than that of CNS. This study emphasizes the crucial role of atomic‐scale interface regulation and intrinsic electric fields in Z‐Scheme VDW heterojunctions, contributing to ameliorative photocatalytic performance.