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<p>Cyclohexanone oxime (CHO) is a pivotal feedstock for plastic manufacturing. However, conventional synthetic routes are fraught with high explosion risks, harsh reaction conditions, and expensive catalysts. Herein, we introduce an electrocatalytic approach to CHO synthesis via the reductive coupling of cyclohexanone (CYC) with nitrite using commercially available Bi<sub>2</sub>O<sub>3</sub> as the catalyst. The method includes a two-stage pulsed electrolysis, where the first stage involves the preparation of amorphous Bi<sub>2</sub>O<sub>3</sub>, and CHO is produced (a Faradaic efficiency of 74.63% and a yield rate of 0.156 mmol h<sup>−1</sup> cm<sup>−2</sup>) from the reaction of CYC and NH<sub>2</sub>OH on stable Bi<sub>2</sub>O<sub>3</sub> during the second stage. Experiments and theoretical calculations on the electrocatalytic nitrite reduction suggest that instead of the *NOH→*N pathway to form NH<sub>3</sub>, the formation of NH<sub>2</sub>OH via the hydrogenation of * NOH is favored on amorphous Bi<sub>2</sub>O<sub>3</sub>. This work offers a sustainable and efficient alternative to conventional CHO synthesis methods.</p>

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Pulsed-electrolysis-induced Bi-Bi2O3 transformation switches the reaction pathway for enhanced cyclohexanone oxime production

  • 期刊论文

  • 发表日期：

    2026年5月20日

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  • Junchao Yu,
  • Zichao Xi,
  • Peng Jing,
  • Xuan Xu,
  • Baocang Liu,
  • Jun Zhang

摘要

Cyclohexanone oxime (CHO) is a pivotal feedstock for plastic manufacturing. However, conventional synthetic routes are fraught with high explosion risks, harsh reaction conditions, and expensive catalysts. Herein, we introduce an electrocatalytic approach to CHO synthesis via the reductive coupling of cyclohexanone (CYC) with nitrite using commercially available Bi2O3 as the catalyst. The method includes a two-stage pulsed electrolysis, where the first stage involves the preparation of amorphous Bi2O3, and CHO is produced (a Faradaic efficiency of 74.63% and a yield rate of 0.156 mmol h−1 cm−2) from the reaction of CYC and NH2OH on stable Bi2O3 during the second stage. Experiments and theoretical calculations on the electrocatalytic nitrite reduction suggest that instead of the *NOH→*N pathway to form NH3, the formation of NH2OH via the hydrogenation of * NOH is favored on amorphous Bi2O3. This work offers a sustainable and efficient alternative to conventional CHO synthesis methods.