Abstract
FTIR spectroscopy was used to identify the oxochloride species of tantalum(V) in ionic liquids and to confirm the correlations between their presence in electrolytes and the changes in the route of electrochemical reduction of tantalum(V). Electrochemical behaviour of the mixtures ( x)1-butyl-1-methyl-pyrrolidinium chloride-(1 − x)TaCl 5 at x = 0.80, 0.65, and 0.40 was investigated over the temperature range 90–160 °C with respect to the electrochemical deposition of tantalum and was discussed in terms of spectroscopic data. The mechanism of electrochemical reduction of tantalum(V) in the basic and acidic electrolytes depends strongly on the structure and composition of the electro active species of tantalum(V) defined by the molar composition of ionic liquids and on the competition between tantalum(V) chloride and oxochloride species. In the basic mixture at x = 0.80, with octahedral [TaCl 6] − ions as the electrochemically active species only the first reduction step Ta 5+ → Ta 4+ at −0.31 V was observed. The competitive reduction of tantalum(V) oxochloride species occurs at more anodic potential (−0.01 V) than the reduction of the chloride complexes and can restrict the further reduction of tantalum(IV). In the basic ionic liquid at x = 0.65, the cyclic voltammograms exhibit reduction peaks at −0.31 V and −0.51 V attributed to the diffusion controlled process as [TaCl 6] − + e − → [TaCl 6] 2− and [TaCl 6] 2− + e − → [TaCl 6] 3−. The further irreversible reduction of tantalum(III) to metallic state may occur at −2.1 V. In the acidic ionic liquids, at x = 0.40 the electrochemical reduction of two species occurs, TaCl 6 − and Ta 2Cl 11 − and it is limited by two electron transfer for both of them at −0.3 V and −1.5 V, respectively.
Published Version
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