A Stable Polyoxovanadate-based Metal-organic Framework Containing Dual Catalytic Sites for Efficient Synthesis of p-benzoquinones.

Chemistry

Key Laboratory of Polyoxometalate and Reticular Material Chemistry of the Ministry of Education, College of Chemistry, Northeast Normal University, Changchun, Jilin, 130024, P. R. China.

Published: April 2025


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Article Abstract

A novel polyoxovanadate-based metal-organic framework (POV-MOF), [Cu(bix)]{VO} (V-Cu-MOF, bix=1,4-bis(imidazol-1-ylmethyl)benzene), has been successfully synthesized and characterized. The V-Cu-MOF demonstrates exceptional performance in the selective oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone within just 10 minutes under mild conditions using hydrogen peroxide as the oxidant. The V-Cu-MOF exhibits remarkable versatility, efficiently oxidizing various substituted phenols while maintaining high catalytic activity. Additionally, it shows excellent recyclability, with conversion and selectivity consistently exceeding 97 % after multiple cycles. Mechanistic studies reveal that the reaction benefits from dual-active centers {VO} clusters and binuclear copper units. The weak substrate adsorption by binuclear copper prevents catalyst poisoning, ensuring sustained activity throughout the process.

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http://dx.doi.org/10.1002/chem.202500255DOI Listing

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