A Stable Polyoxovanadate‐based Metal−organic Framework Containing Dual Catalytic Sites for Efficient Synthesis of p–benzoquinones

Abstract A novel polyoxovanadate‐based metal−organic framework (POV‐MOF), [Cu(bix)]{V 2 O 6 } ( 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 {V 2 O 6 } 2− clusters and binuclear copper units. The weak substrate adsorption by binuclear copper prevents catalyst poisoning, ensuring sustained activity throughout the process.