Contact theorems for electrolyte-filled hollow charged nanoparticles: Non-linear osmotic pressure in confined electrolytes

Abstract

Analytical expressions for the osmotic pressure of electrolytes confined within electrolyte-filled, hollow, charged nanoparticles are studied using contact theorems for cavity nanoshells immersed in a low-concentration electrolyte. Three shell geometries are considered: planar, cylindrical, and spherical. The nanoparticles are modeled as charged cavities of internal radius R and wall thickness d, and are assumed to be at infinite dilution in the surrounding bulk electrolyte. Numerical calculations of the osmotic pressure are presented as a function of several model parameters. For cylindrical and spherical shells, the osmotic pressure exhibits absolute maxima as a function of shell size. This behavior arises from the competition between the violation of the local electroneutrality condition (VLEC) within the shell cavity and the nonlinear profile of the effective electric field. In contrast, the osmotic pressure of the planar (slit-shell) geometry is a monotonic, nonlinear, decreasing function of cavity width. The results are analyzed in terms of the steric and electrostatic (Maxwell stress tensor) contributions appearing in the corresponding contact theorems. Because the analysis is restricted to low surface charge densities and low electrolyte concentrations, the electric double layers (EDLs) inside and outside the shells are obtained from analytical solutions of the linearized Poisson-Boltzmann equation. We report two novel phenomena: confinement charge reversal (CCR) and confinement overcharging (CO). These arise naturally from the topology of the system. By construction, the confined and bulk electrolytes are maintained at the same chemical potential. These findings have implications for the design of synthetic nanocapsules and ion-selective membranes.