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<p>Photosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) via oxygen reduction reaction (ORR) and water oxidation reaction (WOR) pathways requires controlled formation of radical intermediates. However, achieving precise control over radical formation in metal-free catalysts remains challenging. Herein, we report a fluorinated COF (Kf-F-COF) featuring framework-bound carbonyl groups as intrinsic radical-generating sites for efficient dual-channel H<sub>2</sub>O<sub>2</sub> photosynthesis. This design enables the simultaneous activation of O<sub>2</sub> and H<sub>2</sub>O through radical-mediated hydrogen atom transfer processes. Mechanistic studies reveal that fluorination enhances the electron affinity of the carbonyl sites, facilitates diradical formation, and lowers the energy barriers of key reaction steps. As a result, Kf-F-COF achieves a high H<sub>2</sub>O<sub>2</sub> production rate of 6.42 mmol g<sup>−1</sup> h<sup>−1</sup> and long-term stability under natural sunlight and seawater conditions. This work presents a framework-centered radical strategy for dual-pathway H<sub>2</sub>O<sub>2</sub> photosynthesis and offers mechanistic insights into regulating COF-based photocatalysts.</p>

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Fluorinated covalent organic frameworks enable photocatalytic H2O2 production via a photoinduced framework radical pathway

  • 期刊论文

  • 发表日期：

    2025年8月8日

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  • Weixue Tao,
  • Yuchen Wang,
  • Linghui Cong,
  • Chenhui Zhang,
  • Yan Gao,
  • Haifeng Zheng,
  • Wenjie Shi,
  • Dichang Zhong,
  • Tongbu Lu

摘要

Photosynthesis of hydrogen peroxide (H2O2) via oxygen reduction reaction (ORR) and water oxidation reaction (WOR) pathways requires controlled formation of radical intermediates. However, achieving precise control over radical formation in metal-free catalysts remains challenging. Herein, we report a fluorinated COF (Kf-F-COF) featuring framework-bound carbonyl groups as intrinsic radical-generating sites for efficient dual-channel H2O2 photosynthesis. This design enables the simultaneous activation of O2 and H2O through radical-mediated hydrogen atom transfer processes. Mechanistic studies reveal that fluorination enhances the electron affinity of the carbonyl sites, facilitates diradical formation, and lowers the energy barriers of key reaction steps. As a result, Kf-F-COF achieves a high H2O2 production rate of 6.42 mmol g−1 h−1 and long-term stability under natural sunlight and seawater conditions. This work presents a framework-centered radical strategy for dual-pathway H2O2 photosynthesis and offers mechanistic insights into regulating COF-based photocatalysts.