The kinetics of the Cu/Cu redox couple in deep eutectic solvents

Kinetics of electron transfer of the Cu(I)/Cu(II) redox couple at a platinum electrode has been studied with chronoamperometry, cyclic voltammetry and impedance spectroscopy in a deep eutectic solvent consisting of choline chloride and ethylene glycol. At 25 °C, the reaction was found to be quasi-reversible with a relatively high rate constant k⁰ of 9.5 ± 2 × 10⁻⁴ cm s⁻¹, and a charge transfer coefficient α of 0.25 ± 0.05. Diffusion coefficients for the Cu(I) and Cu(II) complexes were determined to be 2.7 ± 0.1 × 10⁻⁷ and 1.5 ± 0.1 × 10⁻⁷ cm² s⁻¹, respectively. The viscosity of the electrolyte was 41 ± 3 mPa s. The temperature dependency was also investigated. The activation energy of mass transfer was found to be 27.7 ± 1 kJ mol⁻¹ and that of electron transfer 39 ± 7 kJ mol⁻¹. Speciation of the Cu(I) and Cu(II) complexes was determined using UV–VIS spectroscopy, and the prevailing Cu(I) complex was found to be [CuCl₃]²⁻ and that of Cu(II) [CuCl₄]²⁻.