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<p>Selective C–N bond formation under mild conditions remains a formidable challenge in sustainable amide synthesis. Conventional approaches are associated with high energy consumption and environmental burden, while the emerging electrochemical strategies are constrained by poor selectivity and low Faradaic efficiency. Here, a redox-cooperative photocatalytic route is developed using a dual-active-site catalyst, where CoO<sub><i>x</i></sub> nanoclusters (NCs) are anchored at oxygen vacancies (OVs) on TiO<sub>2</sub>, spatially decoupling oxidation and reduction reactions. Specifically, CoO<sub><i>x</i></sub> sites catalyze the NO<Stack> <sub>2</sub> <sup>−</sup> </Stack> reduction to generate long-lived <sup>·</sup>NO radicals, while CH<sub>3</sub>CH<sub>2</sub>OH oxidation at OVs yields short-lived CH<sub>3</sub>CH<sub>2</sub>O<sup>·</sup> radicals. The proximity and complementarity of the separated sites enable efficient radical-radical coupling toward acetamide production. This system achieves a high acetamide yield of 38.27 mmol g<sup>−1</sup> h<sup>−1</sup> with excellent selectivity (&gt;92%), alongside superior long-term stability. Mechanistic investigations using <i>in-situ</i> electron paramagnetic resonance (EPR), attenuated total reflectance Fourier-transform infrared (ATR-FTIR), and isotope-labeled analyses reveal the pathways of generation and coupling of reactive intermediates. This work establishes a spatially controlled dual-site platform for efficient photocatalytic C–N coupling, offering a promising paradigm for solar-driven amide synthesis.</p>

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CoOx nanoclusters confined at oxygen vacancies as dual-active sites for acetamide synthesis from photocatalytic redox-enhanced C–N coupling

  • 期刊论文

  • 发表日期：

    2025年11月4日

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  • Huimin Dan,
  • Xin Li,
  • Jieyuan Li,
  • Shujie Shen,
  • Lingling Liu,
  • Luyao Wang,
  • Fan Dong

摘要

Selective C–N bond formation under mild conditions remains a formidable challenge in sustainable amide synthesis. Conventional approaches are associated with high energy consumption and environmental burden, while the emerging electrochemical strategies are constrained by poor selectivity and low Faradaic efficiency. Here, a redox-cooperative photocatalytic route is developed using a dual-active-site catalyst, where CoOx nanoclusters (NCs) are anchored at oxygen vacancies (OVs) on TiO2, spatially decoupling oxidation and reduction reactions. Specifically, CoOx sites catalyze the NO 2 − reduction to generate long-lived ·NO radicals, while CH3CH2OH oxidation at OVs yields short-lived CH3CH2O· radicals. The proximity and complementarity of the separated sites enable efficient radical-radical coupling toward acetamide production. This system achieves a high acetamide yield of 38.27 mmol g−1 h−1 with excellent selectivity (>92%), alongside superior long-term stability. Mechanistic investigations using in-situ electron paramagnetic resonance (EPR), attenuated total reflectance Fourier-transform infrared (ATR-FTIR), and isotope-labeled analyses reveal the pathways of generation and coupling of reactive intermediates. This work establishes a spatially controlled dual-site platform for efficient photocatalytic C–N coupling, offering a promising paradigm for solar-driven amide synthesis.