<p>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<sub>2</sub>S<sub>4</sub> heterostructure integrating an inner CoO<sub>x</sub> nanocage and atomically dispersed Pt anchoring at surface S vacancies for hydrogen evolution from natural seawater (23.88 mmol g<sup>−1</sup> h<sup>−1</sup>) and pure water (48.99 mmol g<sup>−1</sup> h<sup>−1</sup>) under visible light. The dynamic Co<sup>2+</sup>/Co<sup>3+</sup> self-reconstruction of the inner CoOx cage effectively consumes photogenerated holes, while the outer Pt<sub>1</sub> 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<sub>1</sub>-ZnIn<sub>2</sub>S<sub>4</sub>@CoO<sub>X</sub> 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.</p>

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Light-induced CoOX surface reconstruction in hollow heterostructure for durable photocatalytic seawater splitting

  • Chunyu Yuan,
  • Hongfei Yin,
  • Jing Li,
  • Yuxi Zhang,
  • Hongji Chen,
  • Dongdong Xiao,
  • Qizhao Wang,
  • Yongzheng Zhang,
  • Qi-Kun Xue

摘要

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 ZnIn2S4 heterostructure integrating an inner CoOx 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 Co2+/Co3+ self-reconstruction of the inner CoOx cage effectively consumes photogenerated holes, while the outer Pt1 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 Pt1-ZnIn2S4@CoOX 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.