Kinetics of ion transfer at the ionic liquid/water nanointerface.

Ion transfer (IT) processes in ionic liquids (ILs) are essential for their applications in electrochemical systems and chemical separations. In this Article, the first measurements of IT kinetics at the IL/water interface are reported. Steady-state voltammetry was performed at the nanometer-sized polarizable interface between water and ionic liquid, [THTDP(+)][C(4)C(4)N(-)], immiscible with it that was formed at the tip of a nanopipet. Kinetic measurements at such interfaces are extremely challenging because of slow mass-transfer rates in IL, which is ∼700 times more viscous than water. The recently developed new mode of nanopipet voltammetry, common ion voltammetry, was used to overcome technical difficulties and ensure the reliability of the extracted kinetic parameters of IT. The results suggest that the rate of interfacial IT depends strongly on solution viscosity. Voltammetric responses of nanopipets of different radii were analyzed to evaluate the effect of the electrical double layer at the liquid/liquid interface on IT kinetics. The possibility of the influence of the charged pipet wall on ion transport was investigated by comparing currents produced by cationic and anionic species. Possible effects of relaxation phenomena at the IL/water interface on IT voltammograms have also been explored.