Voltammetric study on the behaviour of refractory metals in ([BMP][TFSA]) ionic liquid

MAIS, LAURA;MASCIA, MICHELE;VACCA, ANNALISA;PALMAS, SIMONETTA;DELOGU, FRANCESCO

2014-01-01

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Abstract

Electrochemical studies of tantalum fluoride and zirconium fluoride in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide ([BMP][TFSA]) ionic liquid were carried out in presence of lithium fluoride using cyclic voltammetry technique. The electrochemical behaviour of Ta(V) and Zr(IV) on gold and platinum substrates was investigated in the temperature range from R.T. to 200°C at different values of scan rate and different potential windows. Special attention was paid to the mechanism of cathodic reduction. Cyclic voltammetries exhibit well-defined peaks attributed to the formation of metallic deposits on the substrates. The knowledge of electrode and chemical reactions based on the experimental results of the refractory metals considered allow us to propose a possible reaction path for the oxidation/reduction processes. The mechanisms of electrochemical reduction of Tantalum(V) depends strongly on the composition of the bath; using TaF5 as metal salt, two cathodic peaks due to Ta(V)/Ta(III) and Ta(III)/Ta reduction were observed. The cyclic voltammograms recorded at different values of scan rate have shown that the Ta(III)/Ta reduction process is mainly controlled by diffusion of the electroactive species to the electrode surface. It has been proposed that the mechanism for reduction of zirconium ions occurs in a one step process exchanging four electrons and controlled by the zirconium ions diffusion in the ionic liquid.