Angstrom‐scale channels with versatile ion‐membrane interactions enabling precise ion separation via electrodialysis

Abstract In nature, efficient and selective ion transport is facilitated by ion‐conductive channels in cell membranes; these channels reveal an architectural design with specialized functionality. Drawing inspiration from this, mechanistic insights into the angstrom‐scale‐channel membrane composed of ionic‐crosslinked polybenzimidazole and sulfonated poly(ether ether ketone), exhibiting functional differentiation and efficient ion‐sieving properties are presented. Nanochannels allow for strong hydrogen‐bonding interactions with hydrated ions of higher polarity, while rendering significant electrostatic charge effects that impede the transition of multivalent ions by compressing effective passageways. Both hydrogen bonding and electrostatic interactions synergistically result in high selectivity for monovalent ions over multivalent ions because the latter requires overcoming higher energy barriers for transport compared with the former, thereby causing varying extents of ion dehydration within the nanochannels. The resulting membrane achieves a high monovalent ion permeation rate of 1.35 mol m −2 h −1 with a high mono/multivalent ion selectivity of 56.5 for K + /Mg 2+ and 286 for K + /Al 3+ .