Specific ion effects on electrocapillarity in aqueous electrolytes confined within nanochannels

Abstract

A nanoslit is a long, extremely narrow (nanometers apart) opening between two parallel plates. An overlapped electric double layer is formed when an electrolyte is present inside the slit and there exist distributions of the osmotic pressure and the Maxwell stress across the nanoslit, which lead to the electrocapillarity effect. This feature can be incorporated with the specific ion effects by considering the nonelectrostatic interactions between ions and confining walls, as they significantly influence the potential, electric field, and ion distributions across the nanoslit. In the present work, the electromechanical approach is integrated with the concept of specific ion effects to analyze the behavior of an electrolyte confined in a one-dimensional nanochannel. For a nanochannel, the average outward normal stress exerted on the cross section of a channel (P_{zz}[over ¯]) can be regarded as a measure of electrocapillarity and it is the driving force of the flow. This electrocapillarity measure is analyzed by using the solution of the modified Poisson-Boltzmann equation as a function of the bulk concentration of the electrolyte, the boundary potential, and most importantly, the ion-specific interfacial interactions. The significance of the present work can be manifested by the increasing usage of extremely narrow channels in nanoscaled systems, which will require proper consideration of specific ion effects in determining the behavior of the confined electrolyte.