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<p>Selective electrochemical water oxidation via a 2e<sup>−</sup> pathway represents a sustainable H<sub>2</sub>O<sub>2</sub> electrosynthesis route. However, the low activity and selectivity due to competing 4e<sup>−</sup> oxygen evolution and challenges in separating in-situ-generated H<sub>2</sub>O<sub>2</sub> for subsequent reactions. Herein, we develop an unsaturated coordinative bismuth-benzene tricarboxylic acid metal-organic framework using a hetero-linker doping strategy. The catalyst demonstrates enhanced performance in selective H<sub>2</sub>O<sub>2</sub> synthesis, achieving a low overpotential of 0.98 V and high selectivity with a Faradaic efficiency of 79.1%. The accumulated ~6.17 wt.% H<sub>2</sub>O<sub>2</sub> enables an efficient direct conversion of butanone ammoximation to butanone oxime, showing a high conversion rate of 80.2% and a selectivity of 81.1%. Structural characterizations reveal the unsaturated coordination in the central bismuth atoms. These unsaturated coordinative bismuth sites modulate the OH* intermediate adsorption and optimize the free energy of OH* → H<sub>2</sub>O<sub>2</sub>, as revealed by in-situ attenuated total reflection Fourier transform infrared spectroscopy and theoretical calculations. This work provides a strategy for rationalizing selective 2e<sup>−</sup> water oxidation catalysts and advances the industrially valuable reaction for value-added chemicals production.</p>

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Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月29日

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  • Fan He,
  • Yingnan Liu,
  • Xianyun Peng,
  • Yaqi Chen,
  • Qiang Zheng,
  • Bin Yang,
  • Zhongjian Li,
  • Qiang Zhou,
  • Qinghua Zhang,
  • Jianguo Lu,
  • Lecheng Lei,
  • Gang Wu,
  • Yang Hou

摘要

Selective electrochemical water oxidation via a 2e− pathway represents a sustainable H2O2 electrosynthesis route. However, the low activity and selectivity due to competing 4e− oxygen evolution and challenges in separating in-situ-generated H2O2 for subsequent reactions. Herein, we develop an unsaturated coordinative bismuth-benzene tricarboxylic acid metal-organic framework using a hetero-linker doping strategy. The catalyst demonstrates enhanced performance in selective H2O2 synthesis, achieving a low overpotential of 0.98 V and high selectivity with a Faradaic efficiency of 79.1%. The accumulated ~6.17 wt.% H2O2 enables an efficient direct conversion of butanone ammoximation to butanone oxime, showing a high conversion rate of 80.2% and a selectivity of 81.1%. Structural characterizations reveal the unsaturated coordination in the central bismuth atoms. These unsaturated coordinative bismuth sites modulate the OH* intermediate adsorption and optimize the free energy of OH* → H2O2, as revealed by in-situ attenuated total reflection Fourier transform infrared spectroscopy and theoretical calculations. This work provides a strategy for rationalizing selective 2e− water oxidation catalysts and advances the industrially valuable reaction for value-added chemicals production.