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Major-auxiliary cooperative metal pairs in MOFs enable cascade oxidation of KA oil to ε-caprolactone

Author

Listed:
  • Guangxin Xue

    (National Center for Nanoscience and Technology)

  • Hanlin Liu

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

  • Wei Liu

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

  • Caoyu Yang

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

  • Zhiyong Ban

    (National Center for Nanoscience and Technology)

  • Pengfei An

    (Institute of High Energy Physics, Chinese Academy of Sciences)

  • Wenxing Chen

    (Beijing Institute of Technology)

  • Lirong Zheng

    (Institute of High Energy Physics, Chinese Academy of Sciences)

  • Guodong Li

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

  • Ting Tan

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

  • Zhiyong Tang

    (National Center for Nanoscience and Technology
    University of Chinese Academy of Sciences)

Abstract

Direct oxidation of KA oil (the mixture of cyclohexanone and cyclohexanol) toward ε-caprolactone is in high demand yet hard to implement in need of juggling the activation of both methyne C-H bond of cyclohexanol and α-C-C bond of cyclohexanone. Here we demonstrate that in situ formed Cu1+δ-Oδ-• active site, which originates from relay reaction at Ni(II) and Cu(I) pairs in a metal-organic framework (known as NiCu-MOF-74) with O2 and benzaldehyde (PhCHO), efficiently oxidizes KA oil toward ɛ-caprolactone along with good stability. Mechanism investigation discloses that the auxiliary Ni(II) site first adsorbs O2 for abstracting formyl hydrogen in PhCHO followed by transfer of PhCO· to react with another O2 over the major Cu(I) site, leading to formation of Cu1+δ-Oδ-• and PhCOOH. This major-auxiliary cooperative strategy will be particularly suitable for multivariate MOFs as next generation catalysts towards complex reactions.

Suggested Citation

  • Guangxin Xue & Hanlin Liu & Wei Liu & Caoyu Yang & Zhiyong Ban & Pengfei An & Wenxing Chen & Lirong Zheng & Guodong Li & Ting Tan & Zhiyong Tang, 2024. "Major-auxiliary cooperative metal pairs in MOFs enable cascade oxidation of KA oil to ε-caprolactone," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-54064-w
    DOI: 10.1038/s41467-024-54064-w
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