The Effect of Electrolyte Properties on Ionic Transport through Solid-State Nanopores: Experiment and Simulation

• Published in: Langmuir Vol. 40; no. 40; pp. 20888 - 20896
• Main Authors: Kiy, Alexander, Dutt, Shankar, Gregory, Kasimir P., Notthoff, Christian, Toimil-Molares, Maria Eugenia, Kluth, Patrick
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.10.2024
• ISSN: 0743-7463; 1520-5827; 1520-5827
• DOI: 10.1021/acs.langmuir.4c01347

Nanopore membranes enable versatile technologies that are employed in many different applications, ranging from clean energy generation to filtration and sensing. Improving the performance can be achieved by conducting numerical simulations of the system, for example, by studying how the nanopore geometry or surface properties change the ionic transport behavior or fluid dynamics of the system. A widely employed tool for numerical simulations is finite element analysis (FEA) using software, such as COMSOL Multiphysics. We found that the prevalent method of implementing the electrolyte in the FEA can diverge significantly from physically accurate values. It is often assumed that salt molecules fully dissociate, and the effect of the temperature is neglected. Furthermore, values for the diffusion coefficients of the ions, as well as permittivity, density, and viscosity of the fluid, are assumed to be their bulk values at infinite dilution. By performing conductometry experiments with an amorphous SiO2 nanopore membrane with conical pores and simulating the pore system with FEA, it is shown that the common assumptions do not hold for different mono- and divalent chlorides (LiCl, NaCl, KCl, MgCl2, and CaCl2) at concentrations above 100 mM. Instead, a procedure is presented where all parameters are implemented based on the type of salt and concentration. This modification to the common approach improves the accuracy of the numerical simulations and thus provides a more comprehensive insight into ion transport in nanopores that is otherwise lacking.