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<p>Covalent organic frameworks (COFs) are promising photocatalysts for H<sub>2</sub>O<sub>2</sub> photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumulation, thereby decreasing efficiency. Here, we report T-C type COFs (T = trap units, C = catalytic units), demonstrating that units with keto-enol tautomerism can serve as dynamic electron/hole traps (T) to mitigate Coulomb forces. This design effectively facilitates swift charge transfer and extends carrier lifetimes, thereby enhancing reactions at the C units. Imine COFs derived from 2,4,6-trihydroxybenzaldehyde (Tp) outperform those based on 1,3,5-benzenetricarboxaldehyde due to tautomerization. The optimal Tp COF (TpBpy) achieves an H<sub>2</sub>O<sub>2</sub> generation rate of 37.9 μmol h⁻¹ (or&#xa0;8350 μmol h⁻¹ g⁻¹) under simulated light,&#xa0;and a solar-to-chemical conversion efficiency of 0.038% in a flow reactor under natural sunlight. This work provides molecular design strategies and standard criteria for efficient H<sub>2</sub>O<sub>2</sub> photocatalysts.</p>

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Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年8月12日

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  • Fang Ma,
  • Tao Gao,
  • Xiaodong Sun,
  • Chunqiu Han,
  • Yongye Wang,
  • Anqiang Jiang,
  • Ying Zhou,
  • Guijie Liang,
  • Huiqing Wang,
  • Li Wang,
  • Binbin Jia,
  • Yingping Huang,
  • Hongwei Huang,
  • Xin Ying Kong,
  • Hui Li,
  • Niu Huang,
  • Tianyi Ma,
  • Liqun Ye

摘要

Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumulation, thereby decreasing efficiency. Here, we report T-C type COFs (T = trap units, C = catalytic units), demonstrating that units with keto-enol tautomerism can serve as dynamic electron/hole traps (T) to mitigate Coulomb forces. This design effectively facilitates swift charge transfer and extends carrier lifetimes, thereby enhancing reactions at the C units. Imine COFs derived from 2,4,6-trihydroxybenzaldehyde (Tp) outperform those based on 1,3,5-benzenetricarboxaldehyde due to tautomerization. The optimal Tp COF (TpBpy) achieves an H2O2 generation rate of 37.9 μmol h⁻¹ (or 8350 μmol h⁻¹ g⁻¹) under simulated light, and a solar-to-chemical conversion efficiency of 0.038% in a flow reactor under natural sunlight. This work provides molecular design strategies and standard criteria for efficient H2O2 photocatalysts.