Structurally characterised vanadium(V)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(V)/V(IV) redox couple
作者： Tadaharu Ueda , Jun-ichi Nambu , Jinzhen Lu , Si-Xuan Guo , Qi Li
DOI: 10.1039/C3DT53161A
关键词:
摘要: Structures of the n-tetrabutylammonium salts [SVM11O40]3− (M = Mo, W) have been determined by X-ray crystallography and exhibit 3D networks with V atom disordered over several sites. The cyclic voltammetric behavior SVM11 in neutral acidified acetonitrile solutions also has investigated respect to VV/VIV couple. Results interpreted conjunction data provided 51V NMR spectroscopy on oxidized VV form EPR reduced VIV form. Based mechanistic details inferred from these studies, simulations voltammograms undertaken results compared experimental acidic media (two protonated forms) order provide estimates equilibrium kinetic parameters. For couple series [XVM11O40]n− (X Si,Ge,P,As,S; M Mo,W), reversible potentials linearly depend total charge vanadium-substituted polyoxometalates, similar dependence previously reported for non-substituted parent Keggin polyoxometalates [XM12O40]m−.
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