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HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin
Published on: July 23, 2016
Polyoxovanadate Building Units in Metal-Organic Frameworks: Coordination Connectivity and Selective Oxidation of
Shuang Yu1, Hui-Li Guo1, Bo-Jun Yang1
1Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Molecular Sciences, State Key Laboratory of Green Chemical Synthesis and Conversion, Henan University, Kaifeng 475004, PR China.
Abstract:
Polyoxovanadate (POV) clusters, with their diverse vanadium-oxo coordination modes, provide structurally well-defined inorganic nodes for constructing functional metal-organic frameworks (MOFs). In this work, four polyoxovanadate-based metal-organic frameworks [Co2(DPP)4(V4O12)]·0.25H2O (1), [M3(DPP)4(H2O)4(V6O18)]·2H2O (M = Co (2) and Ni (3)), and [Zn3(DPP)3(V6O18)] (4) (DPP = 1,3-Di(4-pyridyl)propane) were reported and structurally characterized by single-crystal X-ray diffraction. These materials feature distinct POV motifs, including cyclic {V4} units and extended {V3}/{V6} vanadium-oxo chains, providing well-defined coordination environments around the metal nodes. All four MOFs efficiently catalyzed the oxidation of aromatic thioethers using H2O2 with high selectivity for sulfoxide formation. Among them, compound 4 exhibited the highest activity and excellent recyclability over at least five cycles, consistent with its robust structural stability. Comparative catalytic and structural analyses suggest that the superior performance of 4 originates from the parallel and independent action of unsaturated V and Zn centers within its zigzag V-Zn chains. This study demonstrates that tuning POV building units and their coordination connectivity provides an effective strategy for controlling activity and selectivity in oxidation reactions.
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