Chem. J. Chinese Universities

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Sustainable epoxidation of cycloalkenes using air catalyzed by bimetallic CuCo-MOFs

CHENG Rou, SUN Fanqi, LU Xinhuan, GUO Haotian, ZHAN Junhui, HUANG Jia, YAN Shan, ZHOU Dan, XIA Qinghua   

  1. Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals, Hubei University
  • Received:2025-08-21 Revised:2025-09-23 Online First:2025-09-25 Published:2025-09-25
  • Contact: LU Xinhuan E-mail:xinhuan003@aliyun.com
  • Supported by:
    Supported by the National Natural Science Foundation of china (Nos. 22072038, 22272045) and the Open Funding Project of Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals, China (No. HKLB2414)

Abstract: Bimetallic metal-organic frameworks (MOFs) possess tunable skeletal structures and synergistic effects between multiple metals, demonstrating significant application potential in the field of catalysis. In this study, Cu2+ and Co2+, which have similar electronic structures and ionic radii, were selected as metal centers to successfully construct a bimetallic CuCo-MOF catalyst, achieving efficient and mild air-mediated epoxidation of cycloalkenes without the addition of external initiators or co-reductants. The Cu0.1Co1-MOF-BTC-H catalyst prepared via static hydrothermal method was thoroughly characterized by various techniques including XRD, FE-SEM, XPS and NH3-TPD. Under optimized conditions (using 1,4-dioxane as the solvent, 80 °C, 5 h and air as the oxidant), the catalyst demonstrated excellent catalytic performance in the air-catalyzed epoxidation of 3-methyl-1-cyclohexene, achieving a substrate conversion rate of up to 97.2% and epoxide product selectivity ≥99%. Additionally, the catalyst demonstrates good substrate universality, achieving conversion rates of 79.4% and 80.3% for cyclooctene and 4-vinyl-1-cyclohexene, respectively, with corresponding epoxide product selectivities of 98.0% and 74.3%. After five cycles of use, the catalyst maintains stable catalytic activity, indicating excellent cyclic stability.

Key words: Bimetallic CuCo-MOFs, Cycloolefin, 3-Methyl-1-cyclohexene, Air, Epoxidation

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