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<p>Organic photocatalysts with porphyrin conjugated chromophore core are promising for artificial hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) photosynthesis, but the lack of bottom-up paradigm for oxygen (O<sub>2</sub>) adsorption sites hinders their activity. Here, we introduce imidazole groups as <i>π</i>-electron sites with charge-complementarity to the O<sub>2</sub> molecules, enhancing O<sub>2</sub> binding via sub-atomically mirrored electrostatic cooperative <i>π</i>-<i>π</i> dispersion forces. In situ spectroscopy and theory reveal that the ~2 Å linear δ<sup>+</sup>-δ<sup>−</sup>-δ<sup>+</sup> domain of the imidazole substituent exhibits 2.8-folds stronger O<sub>2</sub> adsorption than neutral <i>π</i>-electron substituents, accompanied by the generation of energetically peroxide intermediates. Consequently, imidazole-substituted porphyrin photocatalysts achieve a solar-to-chemical conversion efficiency of 1.85% using only H<sub>2</sub>O and O<sub>2</sub>. In scalable membranes with photocatalysts, enabling daily photosynthetic production of 80 L m<sup>−2</sup> of Fenton-applicable H<sub>2</sub>O<sub>2</sub> solution. This work offers a strategy to modulate the electrostatic distribution of oxygen photoreduction sites, providing insights into overcoming gas activation rate-limiting steps in photocatalytic processes.</p>

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Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月8日

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  • Yan Guo,
  • Qixin Zhou,
  • Li Wang,
  • Ziqi Deng,
  • David Lee Phillips,
  • Chuyang Y. Tang,
  • Yongfa Zhu

摘要

Organic photocatalysts with porphyrin conjugated chromophore core are promising for artificial hydrogen peroxide (H2O2) photosynthesis, but the lack of bottom-up paradigm for oxygen (O2) adsorption sites hinders their activity. Here, we introduce imidazole groups as π-electron sites with charge-complementarity to the O2 molecules, enhancing O2 binding via sub-atomically mirrored electrostatic cooperative π-π dispersion forces. In situ spectroscopy and theory reveal that the ~2 Å linear δ+-δ−-δ+ domain of the imidazole substituent exhibits 2.8-folds stronger O2 adsorption than neutral π-electron substituents, accompanied by the generation of energetically peroxide intermediates. Consequently, imidazole-substituted porphyrin photocatalysts achieve a solar-to-chemical conversion efficiency of 1.85% using only H2O and O2. In scalable membranes with photocatalysts, enabling daily photosynthetic production of 80 L m−2 of Fenton-applicable H2O2 solution. This work offers a strategy to modulate the electrostatic distribution of oxygen photoreduction sites, providing insights into overcoming gas activation rate-limiting steps in photocatalytic processes.