Abstract
The electrochemistry of monoclinic and tetragonal vanadium-doped zirconias (VZrO2), prepared from gel precursors with vanadium loadings ranging from 0.5 to 15 mol%, has been studied using abrasive-conditioned graphite/polyester composite electrodes immersed in aqueous HCl and HClO4 solutions. Isolated vanadium centers form a solid solution in the zirconia lattice with a solubility limit close to 5 mol%. Above 5 mol%, finely dispersed V2O5 is formed. Vanadium centers located at the boundary sites of the zirconia lattice display successive one-electron transfer processes near to +0.25 and +0.10 V vs. SCE, whereas finely dispersed V2O5 yields three successive reduction processes at +0.46, +0.30, and +0.16 V vs. SCE. Electrochemical data indicate the presence of both V5+ and V4+ centers in the lattice of monoclinic and tetragonal zirconias, the V5+/V4+ ratio decreasing as the vanadium loading increases.
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