Z‐Scheme Modulated Charge Transfer on InVO4@ZnIn2S4 for Durable Overall Water Splitting

The charge transfer within heterojunction is crucial for the efficiency and stability of photocatalyst for overall water splitting (OWS). Herein, InVO4 nanosheets have been employed as a support for the lateral epitaxial growth of ZnIn2S4 nanosheets to produce hierarchical InVO4@ZnIn2S4 (InVZ) heterojunctions. The distinct branching heterostructure facilitates active site exposure and mass transfer, further boosting the participation of ZnIn2S4 and InVO4 for proton reduction and water oxidation, respectively. The unique Z‐scheme modulated charge transfer, visualized by simulation and in situ analysis, has been proved to promote the spatial separation of photoexcited charges and strengthen the anti‐photocorrosion capability of InVZ. The optimized InVZ heterojunction presents improved OWS (153.3 µmol h−1 g−1 for H2 and 76.9 µmol h−1 g−1 for O2) and competitive H2 production (21090 µmol h−1 g−1). Even after 20 times (100 h) of cycle experiment, it still holds more than 88% OWS activity and a complete structure. Ternary metal sulfide/oxide (ZnIn2S4 and InVO4) is chosen for the construction of efficient and stable Z‐scheme heterojunction photocatalyst. The optimized heterojunction presents remarkable overall water splitting and excellent stability. The unique Z‐scheme modulated charge transfer is proved to promote the spatial separation of photoexcited charges and strengthen the anti‐photocorrosion capability of the system.