Constructing Spatially Separated Cage‐Like Z‐scheme Heterojunction Photocatalyst for Enhancing Photocatalytic H2 Evolution

Heterojunctions coupled into micro-mesoscopic structures is an attractive strategy to optimize the light harvesting and carrier separation of semiconductor photocatalysts. A self-templating method of ion exchange is reported to synthesize an exquisite hollow cage-structured Ag₂ S@CdS/ZnS that direct Z-scheme heterojunction photocatalyst. On the ultrathin shell of the cage, Ag₂ S, CdS, and ZnS with Zn-vacancies (V_Zn ) are arranged sequentially from outside to inside. Among them, the photogenerated electrons are excited by ZnS to the V_Zn energy level and then recombine with the photogenerated holes that are generated by CdS, while the electrons remained in the CdS conduction band are further transferred to Ag₂ S. The ingenious cooperation of the Z-scheme heterojunction with the hollow structure optimizes the photogenerated charges transport channel, spatially separated the oxidation and reduction half-reactions, decreases the charge recombination probability, and simultaneously improves the light harvesting efficiency. As a result, the photocatalytic hydrogen evolution activity of the optimal sample is 136.6 and 17.3 times higher than that of cage-like ZnS with V_Zn and CdS by, respectively. This unique strategy demonstrates the tremendous potential of the incorporation of heterojunction construction to morphology design of photocatalytic materials, and also provided a reasonable route for designing other efficient synergistic photocatalytic reactions.