The role of ion-membrane interactions in fast and selective mono/multivalent ion separation with hierarchical nanochannels

Precise control over the nanofluid behavior of polyelectrolyte-based membranes is a primary step toward understanding the structure-morphology-property relationships to ultimately determine the mass transfer characteristics. In this study, a high-performance multistacked polyelectrolyte-based cation exchange membrane (CEM) with a heterogeneous structure and versatile surface chemistry was developed to achieve selective ion conductance. The self-assembled CEM can facilitate ion permeation with fluxes of 2.9 mol m⁻² h⁻¹ for K⁺ and 0.22 mol m⁻² h⁻¹ for Mg²⁺, reaching a mono/multivalent ionic selectivity of up to 13, outperforming mono/divalent fractionation when compared with state-of-the-art membranes. Molecular dynamic (MD) simulations illustrated the ionic transport trajectory in hierarchical channels with angstrom-scale cavities using multilayered CEMs. Both the experimental measurements and theoretical simulations indicated that ionic fractionation was associated with a large disparity in the energy barrier between mono/multivalent cations, which was the primary origin of the differences in the ion dehydration-rehydration processes in the angstrom-confinement membrane ion channels.