Layered Zn₃In₂S₆-Based Nanomaterials for Photocatalytic Hydrogen Production

Photocatalytic water splitting for hydrogen production is recognized as one of the most promising solutions to alleviate global energy crises and mitigate environmental pollution. As a typical ternary chalcogenide semiconductor with a layered structure，Zn₃In₂S₆（ZIS）has garnered significant attention in the field of photocatalytic hydrogen evolution，thanks to its favorable energy band structure，excellent visible-light response capability，and abundant surface active sites. This review comprehensively summarizes the latest research progress of ZIS-based nanomaterials in photocatalytic hydrogen production. First，it systematically elaborates on the fundamental properties of ZIS，including its hexagonal layered crystal structure and its energy band characteristics，as well as the core mechanism of photocatalytic hydrogen production centered on the separation and migration of photogenerated carriers. Then，the review focuses on the application progress of ZIS-based nanomaterials in different photocatalytic hydrogen production systems：overall water splitting （achieving efficient carrier separation via S-scheme heterojunctions），hydrogen production in sacrificial agent systems（optimizing hole consumption paths with agents like lactic acid，formic acid，and triethanolamine to enhance efficiency），and bifunctional coupled reaction systems（including organic pollutant degradation coupled with hydrogen production，selective oxidation of alcohols such as benzyl alcohol and 5-hydroxymethylfurfural coupled with hydrogen production，and hydrogen peroxide synthesis coupled with hydrogen production）. For each system，a comparative analysis is conducted on reaction mechanisms，advantages，disadvantages，performance optimization strategies （e. g. ， heterojunction construction， cocatalyst loading， defect engineering），and technical economy. Finally，the review discusses the current challenges faced by ZIS-based photocatalytic materials，especially in bifunctional coupled reaction systems，such as limited selectivity in organic oxidation，catalyst deactivation，and complex product separation，and proposes future development directions，including the design of atomically dispersed cocatalysts，in situ mechanism studies using advanced characterization technologies，and integration with practical application scenarios like wastewater treatment. This review provides a systematic reference for the rational design and further development of high-performance ZIS-based photocatalytic materials for hydrogen production.