Electrochemistry in Deep Eutectic Solvents

We report the cyclic voltammetry, chronoamperometry, and scanning electrochemical microscopy of ferrocene dissolved in deep eutectic solvents (DES), consisting of choline chloride (ChCl) and either trifluoroacetamide (TFA) or malonic acid as the hydrogen-bond donor. Despite the use of ultramicroelectrodes, which were required due to the modest conductivities of the DES employed, linear diffusion behavior was observed in cyclic voltammetric experiments. The high viscosity of 1:2 ChCl/TFA relative to non-aqueous electrochemical solvents leads to a low diffusion coefficient, 2.7 x 10(-8) cm2 s(-1) for ferrocene in this medium. Because of the difficulties in achieving steady-state conditions, SECM approach curves were tip velocity dependent. Under certain conditions, SECM approach curves to an insulating substrate displayed a positive-feedback response. Satisfactory simulation of this unexpected behavior was obtained by including convection terms into the mass transport equations typically used for SECM theory. The observance of positive-feedback behavior at an insulating substrate can be described in terms of a dimensionless parameter, the Peclet number, which is the ratio of the convective and diffusive timescales. Fitting insulator approach curves of ferrocene in 1:2 ChCl/TFA shows an apparent increase in the diffusion coefficient with increasing tip velocity, which can be explained by DES behaving as a shear thinning non-Newtonian fluid.