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

Guangxin Xue, Hanlin Liu, Wei Liu, Caoyu Yang, Zhiyong Ban, Pengfei An, Wenxing Chen, Lirong Zheng, Guodong Li (), Ting Tan () and Zhiyong Tang ()
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Guangxin Xue: National Center for Nanoscience and Technology
Hanlin Liu: National Center for Nanoscience and Technology
Wei Liu: National Center for Nanoscience and Technology
Caoyu Yang: National Center for Nanoscience and Technology
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
Ting Tan: National Center for Nanoscience and Technology
Zhiyong Tang: National Center for Nanoscience and Technology

Nature Communications, 2024, vol. 15, issue 1, 1-13

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-54064-w

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