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

/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.