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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.202500255 | DOI Listing |
Angew Chem Int Ed Engl
July 2025
College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, 410082, P.R. China.
Following the construction schemes of pyrgoscages and catenanes, attempts to splice polyoxovanadate-based metal-organic polyhedra (POV-MOPs) together have been carried out in this work. To meet the requirements of POV-MOPs with varied sizes, synthetic strategies including reconstruction of original vertex, introduction of exogenous vertex, and initiative of polyhedral interlock have been developed, which successfully integrated a pair of tetrahedral monomers into an hourglass-shaped dimer. On top of this, several structuring principles, such as anisotropic enhancement, electrostatic potential reduction, and sufficient intramolecular support, can be drawn from here and popularized to the related MOP systems.
View Article and Find Full Text PDFEnviron Sci Pollut Res Int
March 2025
Jiangsu Key Laboratory of Pesticide Sciences, Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing, 210095, P. R. China.
A new polyoxovanadates-based metal-organic framework (POV-MOF) Ag(Tipa)(VO) (Ag-V-MOF) with unique curly layered structure has been designed by virtue of a stellated tridentate N-containing ligand of tri-(4-(1-H-imidazol-1-yl)phenyl)amine (Tipa). After effectually alkali-treated by sodium hydroxide solution in certain concentrations, the modified materials, named EA-Ag-V (x = 1, 2, 3, and 4) were obtained expectedly, among which EA-Ag-V exhibited a gratifying performance in adsorption creatinine, a major uremic toxin generated during hemodialysis treatment in patients with renal failure. The maximum adsorption capacity of creatinine was 140.
View Article and Find Full Text PDFChemistry
April 2025
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.
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.
View Article and Find Full Text PDFInorg Chem
November 2024
College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha 410082, P. R. China.
Promoting the advancement of the structure and function of metastable substances is challenging but worthwhile. In particular, how to harness the entangled state and evolution path of labile porous structures has been at the forefront of research in molecular self-assembly. In this work, the metastable structures of polyoxovanadate-based metal-organic polyhedra (VMOPs) can be manually regulated, including separation of the interlocked aggregate by a ligand-widening approach as well as transformation from a tetrahedral to capsule-like scaffold via a vertice-remodeling strategy.
View Article and Find Full Text PDFInorg Chem
June 2024
School of Chemistry, Dalian University of Technology, Dalian 116023, Liaoning, China.
-Benzoquinones are important organic intermediates in the synthesis of biopharmaceuticals and fine chemicals. In this study, two crystalline 3D polyoxovanadate-based metal-organic frameworks, H[Cu(tpi)]{CuVO}·HO (, tpi = CNH) and [Co(Htpi)]{VO} (, Htpi = CNH), were synthesized, which as heterogeneous catalysts showed excellent catalytic activities for the synthesis of -benzoquinones. Both compounds were characterized by IR, UV-vis diffuse reflectance spectroscopy, TG, XPS, X-ray diffraction, etc.
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