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CsCl-type inorganic cluster-based high-symmetry crystal built from {Mo4.55V7.45PO40}10.45− with high ratio of vanadium to molybdenum and {H2O0.3@K6(H2O)12}6+ clusters exhibiting proton conduction below the freezing point of water

Abstract

As a class of anionic oxoclusters of early transition metals in their highest oxidation states, polyoxometalates (POMs) show a myriad structural versatility, unique chemical and physical properties, making them promising multifunctional materials. In this study, a Keggin-type POM has been achieved, with a formula of K6H4.45[PV7.45Mo4.55O40]·nH2O (1), and its microcrystals and nanocrystals were obtained, respectively. This POM was characterized by elemental analysis for C, H and N, ICP-MS, TG, PXRD, SEM, X-band EPR and XPS techniques. The single crystal X-ray diffraction analysis demonstrated that 1 shows rare extended structure with high-connected three-dimensional (3D) all inorganic networks of Keggin-type POM, built from {Mo4.55V7.45PO40}10.45− polyoxoanions and {H2O0.3@K6(H2O)12}6+ clusters with CsCl-type crystal structure. In addition, to the best of our knowledge, 1 shows the highest ratio of vanadium to molybdenum in Keggin-type POMs thus far. Most interestingly, 1 exhibits the intrinsic proton conduction below the freezing point of water, with the proton conductivity of 6.90×10-7 S cm-1 at 249 K and further reaching to 3.36×10-6 S cm-1 at 272 K and Ea = 0.44 eV in 249-272 K.

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Supplementary files

Publication details

The article was received on 08 Oct 2019, accepted on 03 Nov 2019 and first published on 04 Nov 2019


Article type: Paper
DOI: 10.1039/C9DT03960K
Dalton Trans., 2019, Accepted Manuscript

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    CsCl-type inorganic cluster-based high-symmetry crystal built from {Mo4.55V7.45PO40}10.45− with high ratio of vanadium to molybdenum and {H2O0.3@K6(H2O)12}6+ clusters exhibiting proton conduction below the freezing point of water

    Z. Yao, G. Zhang, J. Zhang, J. Liu, L. Liu and X. Ren, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C9DT03960K

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