Abstract
New different series of xV2O3∙(100−x)[4PbO2·Pb] glasses were prepared by melt-quenching method in a wide range of compositions defined by the parameter x=0–30mol% V2O5. InfraRed (IR) data reveal that by increasing the V2O5 content, the glass network was transformed into a mixture of modified [VO4] structural units, namely pyrovanadate and orthovanadate ones. The UltraViolet–Visible (UV–VIS) spectra show that addition of V2O5 produces a gradual shift of the absorption edge towards the higher wavelength side (indicating the increase in concentration of vanadyl species) and a decrease of the gap energy.The shape of the Electron Spin Resonance (ESR) spectra changes with increasing the V2O5 content suggesting that the interactions between vanadium centers strongly depend on x parameter which plays an important role. A hyperfine structure becomes visible in the glass with x=20mol% V2O5 suggesting modifications of the glass structure caused by the network modifier. If the network is moderately disrupted the formation of Pb+2–V+4 pairs was coupled through the oxygen atom or the interactions within V+4–O–V+5 chains mask hyperfine structure.The shape of cyclic voltammograms, redox waves and good reversibility of the x=20mol% V2O5 glassy electrode depends on the electrolyte acidity and electrochemically active species present in the glass network.
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