Cation-ligand interactions dictate salt partitioning and diffusivity in ligand-functionalized polymer membranes

Everett S. Zofchak, Zidan Zhang, Nico Marioni, Tyler J. Duncan, Harnoor S. Sachar, Alyssa Chamseddine, Benny D. Freeman, Venkat Ganesan

Research output: Contribution to journalArticleResearchpeer-review

10 Citations (Scopus)


Membranes are an attractive alternative to current thermal separations due to their scalability and energy efficiency in desalinating water. Unfortunately, many of the conventional membrane materials available today are unable to differentiate between ionic solutes, especially alkali cations, compromising their use in ion-ion separations. Inspired by the ion-specific interactions exhibited by biological ion channels, recent research efforts have focused on synthesizing and characterizing new polymeric materials that incorporate ligands into polymer networks to bias solubility and/or diffusivity of one cationic species over another. Despite these efforts, little is known about the influence of incorporating ligands into polymer membranes on solubility and diffusivity of the complexing species. In this study, we first build a qualitative model of salt partitioning, diffusivity, and permeability in generic cation-complexing ligand-functionalized polymer membranes. Next, to validate our model and hypotheses, we perform atomistic molecular dynamics simulations of a 12-crown-4-functionalized membrane in the presence of alkali halide salts at low concentration. Generally, cation complexation enhances cation solubility but decreases diffusivity. Interestingly, the reduction in diffusivity is predicted to be larger than the enhancement in solubility for materials which operate by the mechanisms proposed in our physical picture, ultimately resulting in a reduction in the permeability of the selectively complexing ion.

Original languageEnglish
Pages (from-to)2260-2270
Number of pages11
Issue number6
Publication statusPublished - 22 Mar 2022
Externally publishedYes

Cite this