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Updated: Feb 20, 2026

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance
Published on: September 5, 2018
Two New Sandwich-Type Polyoxomolybdates Functionalized with Diphosphonates: Efficient and Selective Oxidation of
Qiaofei Xu1, Xiaopeng Sun2, Feng Hu3
1Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China. xqf199408a@163.com.
Abstract:
Two sandwich-type polyoxomolybdates Na₈[MO₂{Mo₂O₅(O₃PCH₃C(O)PO₃)}₂] (M = Ni2+ (1); Co2+ (2)) were synthesized by one-pot reaction of Na₂HPMo12O40·14H₂O, 1-hydroxy ethidene diphosphonic acid (HEDP=HOC(CH₃)(PO₃H₂)₂), and (1) NiCl₂/CoCl₂ (2). Compounds 1 and 2 were characterized by single crystal X-ray analysis, X-ray powder diffraction (XRPD), IR spectroscopy, 31P NMR spectra, UV-vis spectroscopy, and thermogravimetric analyses (TGA). Structural analysis reveals that 1 and 2 exhibit similar centrosymmetric structure, which consists of one transition metal (TM) ion sandwiched by two same subunits {Mo₂O₅(O₃PCH₃C(O)PO₃)}. The clusters 1 and 2 show efficient catalytic activities for oxidation of thioanisole. Moreover, they are catalytically selective for oxidizing thioanisole. Both resuable polyoxomolybdates 1 and 2 catalysts show good thermo- and hydrolytic stability. It is noted that compound 1 shows outstanding catalytic activity for oxidation of various sulfides to corresponding sulfones with 93-100% selectivity at 97-100% conversion in one hour under mild conditions, which is potentially valuable to the removal of organic sulfides.
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