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Revista de Chimie (Rev. Chim.), Year 2014, Volume 65, Issue 3,





ANDA IOANA GRATIELA PETREHELE, DAN RUSU, ALIA UNGUREAN, GRAZIELLA L. TURDEAN, EMIL INDREA, LEONTIN DAVID, MARIANA RUSU
Structural and Physico-Chemical Study of New Keggin Polyoxometalates with Mixed Adenda

Abstract:

Reactions between [a-PVMo10O39]8-, mono-lacunary Keggin monovanado-deca-molybdophosphate and transition metal cations Mn2+, Fe3+, Co2+, Ni2+ and Cu2+ in aqueous solution results in the formation of new polyoxometalate complexes, with the stoichiometry metal : ligand by 1:1. New complexes were isolated as potassium salts, i.e. K8-n[Mn+(H2O)PVMo10O39] ·xH2O. The molecular formula of complexes was determined by elemental and thermo-gravimetric analysis, UV-Vis, FT-IR, Raman, EPR spectroscopy and X-ray diffraction. The investigation results strongly suggest a Keggin-type structure with mixed addenda of new complexes in which the transition metal cations are coordinated by five oxygen atoms of the cavity of lacunary polyoxometalate anions and sixth oxygen atom originates in the water molecule in distorted Oh symmetry. Some of new complexes, K6[Ni(H2O)PVMo10O39 ] . x H2O (x = 16, 21) and K6[Cu(H2O)PVMo10O39] . 17H2O, crystallized in monoclinic system, space group P21/c. The electrocatalytic activity of the K6[Cu(H2O)PVMo10O39] . 17H2O compound towards H2O2 was evidenced. Keywords: Keggin polyoxometalates, FTIR, Raman, EPR spectroscopy, Cyclic voltammetry


Issue: 2014, Volume 65, Issue 3
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