Photocatalytic production of hydrogen peroxide (H 2 O 2 ) has attracted considerable attention as a green and sustainable synthesis route. Herein, a series of ZIS/HBIP type‐I heterojunction composites were fabricated by depositing hexagonal bismuth phosphate (HBIP) onto flower‐like ZnIn 2 S 4 (ZIS) microspheres via a room‐temperature precipitation method and applied to photocatalytic H 2 O 2 synthesis. Under visible light in pure water, ZIS/HBIP achieved an H 2 O 2 production rate of 955 μmol·g −1 ·h −1 . Mechanistic investigations revealed that Fermi‐level equilibration at the heterojunction effectively regulates interfacial charge distribution and utilization, thereby enhancing photochemical efficiency. Compared with pristine ZIS, the ZIS/HBIP composite exhibited an increased contact angle toward H 2 O 2 , indicating reduced interfacial affinity, which suppresses H 2 O 2 adsorption‐decomposition and promotes continuous accumulation. Rotating disk electrode (RDE) tests further confirmed that ZIS/HBIP predominantly produces H 2 O 2 via a direct two‐electron oxygen reduction pathway (2e − ORR), with markedly higher selectivity than the stepwise single‐electron route. This work offers insights into the rational design of efficient and stable photocatalysts by synergistically regulating reaction pathways and product desorption behavior.
Yang et al. (2026) studied this question.