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<p>Nature’s redox enzymes achieve remarkable selectivity by organizing active sites with precise spatial control, an ability difficult to replicate in synthetic systems. Inspired by this, we report a class of stable, metal-free bicarbenium-based molecular catalysts that undergo electrochemical two-electron reduction to form biradical intermediates. These biradicals are confined within a rigid xanthene bridge ( ~ 4.3 Å), creating a spatially defined pocket that engages paramagnetic substrates, such as O₂ and NO, resembling nature’s synergistic catalysis. This biradical-mediated synergistic catalysis enables highly selective two-electron oxygen reduction (99.3% H<sub>2</sub>O<sub>2</sub> selectivity, 96.8% Faradaic efficiency, 2.21 mol g⁻¹<sub>cat</sub> h⁻¹ productivity) and three-electron nitric oxide reduction (NH₂OH as major product, 87.2% Faradaic efficiency, 1.68 mol g<sup>-</sup>¹<sub>cat</sub> h<sup>-</sup>¹ productivity). Experimental and computational studies confirm the sustained redox cycling, supported by favorable spin-pairing and substrate binding geometries, which enhance both catalytic selectivity and efficiency. This work presents a blueprint for pathway-specific, radical-mediated catalysis, offering new design principles for metal-free electrocatalytic platforms that exploit open-shell reactivity.</p>

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Biradical-mediated synergistic electrocatalysis using metal-free redox molecular catalysts

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月13日

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  • Danjun Fu,
  • Jun Zhu,
  • Lulu Wang,
  • Rui Liu,
  • Liuying Jiao,
  • Zhenghao Li,
  • Xiaofei Zhang,
  • Le Yang,
  • Pengfei Ou,
  • Jishan Wu

摘要

Nature’s redox enzymes achieve remarkable selectivity by organizing active sites with precise spatial control, an ability difficult to replicate in synthetic systems. Inspired by this, we report a class of stable, metal-free bicarbenium-based molecular catalysts that undergo electrochemical two-electron reduction to form biradical intermediates. These biradicals are confined within a rigid xanthene bridge ( ~ 4.3 Å), creating a spatially defined pocket that engages paramagnetic substrates, such as O₂ and NO, resembling nature’s synergistic catalysis. This biradical-mediated synergistic catalysis enables highly selective two-electron oxygen reduction (99.3% H2O2 selectivity, 96.8% Faradaic efficiency, 2.21 mol g⁻¹cat h⁻¹ productivity) and three-electron nitric oxide reduction (NH₂OH as major product, 87.2% Faradaic efficiency, 1.68 mol g-¹cat h-¹ productivity). Experimental and computational studies confirm the sustained redox cycling, supported by favorable spin-pairing and substrate binding geometries, which enhance both catalytic selectivity and efficiency. This work presents a blueprint for pathway-specific, radical-mediated catalysis, offering new design principles for metal-free electrocatalytic platforms that exploit open-shell reactivity.