Abstract
Photocorrosion triggered by the unconsumed photogenerated holes severely deteriorates the photocatalytic efficiency and stability of semiconductor photocatalysts, especially in seawater with complex ions. Here, we report a hierarchical hollow ZnIn(2)S(4) heterostructure integrating an inner CoO(x) nanocage and atomically dispersed Pt anchoring at surface S vacancies for hydrogen evolution from natural seawater (23.88 mmol g(-1) h(-1)) and pure water (48.99 mmol g(-1) h(-1)) under visible light. The dynamic Co(2+)/Co(3+) self-reconstruction of the inner CoOx cage effectively consumes photogenerated holes, while the outer Pt(1) single atoms localized at S vacancies serve as electron sinks to facilitate electron extraction and proton reduction. Benefiting from the dynamic hole-scavenging mechanism via oxidation self-reconstruction, the Pt(1)-ZnIn(2)S(4)@CoO(X) photocatalyst exhibits enhanced durability against alkali metal ions in seawater and maintains high reactivity for long-term hydrogen evolution. This work underscores the importance of light-induced transition metal dynamic self-reconstruction within hierarchical hollow heterostructure photocatalysts for sustainable hydrogen evolution.