In Situ Probing Liquid/Liquid Interfacial Kinetics through Single Nanodroplet Electrochemistry.

In this study, we report the new application of single nanodroplet electrochemistry to in situ monitor the interfacial transfer kinetics of electroactive species across liquid/liquid interface. Interfacial kinetic information is crucial in drug delivery and membrane transport. However, interfacial information has been mainly studied thermodynamically, such as partition coefficient, which could not manifest a speed of transfer. Herein, we measure the phase-transfer kinetic constant via the steady-state electrochemistry of an extracted redox species in a single nanodroplet. The redox species were transferred from the continuous oil phase to the water nanodroplet by partition equilibrium. The transferred redox species are selectively electrolyzed within the droplet when the droplet contacts with an ultramicroelectrode, while the electrochemical reaction of the redox species outside the droplet (i.e., organic solvent) is effectively suppressed by adjusting the electrolyte composition. The redox species in the water droplets can quickly attain a steady state during electrolysis owing to an extensive mass transfer by radial diffusion, and the steady-state current can be analyzed to obtain kinetic information with help from the finite-element method. Finally, a quick calculation method is suggested to estimate the kinetic constant of phase transfer without simulation.