Determination Method of Diffusion Coefficient in a Neat Redox-Active Ionic Liquid at a Microdisk Electrode in the Domains Ranging from the Steady-State to Potentiodynamic Near-Steady-State

Abstract

In redox-active ionic liquids (RAILs), either or both of the constituent ions are redox-active. Because of the high concentration of the ions, RAILs exhibit not only ion conduction but also electron conduction through the bimolecular electron self-exchange reaction. Because neat RAILs do not contain any supporting electrolyte, migration of the redox active ions results in enhancement or diminishment of the redox current at an electrode. To treat the migration effect for electrochemical analysis, a limiting current correction was theoretically derived by Oldham, Hyk, and Stojek (Oldham, K. J. Electroanal. Chem. 1992, 337, 91-126; Hyk, W.; Stojek, Z. Anal. Chem. 2002, 747, 4805-4813) for the steady-state voltammetry. Although steady-state voltammetry is a robust method in electrochemistry, the actual measurement is time-consuming and cannot be always made because of the instability of the electrochemical system. To overcome the problem, we propose the use of cyclic voltammetry to evaluate the diffusion coefficient of the redox-active ion that constitutes RAIL. The peak currents were analyzed by the purely diffusional framework of the Aoki-Matsuda-Osteryoung equation (Aoki, K.; Akimoto, K.; Tokuda, K.; Matsuda, H.; Osteryoung, J. J. Electroanal. Chem. 1984, 171, 219-230.) in the range from several mV s^-1 to several ten mV s^-1, and the migration correction to the near-steady-state limiting current was applied on the basis of the Oldham-Hyk-Stojek theory to scale the diffusion coefficient. As an example of RAILs, [FcC₆ImC₁][TFSI], which exhibits charge increase reaction with the same sign (S⁺ - e^- ⇌ P²⁺), was used and the cyclic voltammograms were recorded at various sizes of the microdisk electrodes and various scan rates. The peak currents obeyed the Aoki-Matsuda-Osteryoung equation with the scaled diffusion coefficient, which has the same value as determined by the steady-state voltammogram. Our approach can be used to evaluate the diffusion coefficient of redox-active ions that constitute the RAIL with the charge increase reaction with the same sign.