Ionophore-Based Molecular Layer-by-Layer Polyamide Membranes for Facilitated Single-Ion Transport

Single-ion-selective membranes are indispensable for efficient ion separations in environmental, energy, and biomedical technologies. Inspired by biological ion channels, this work harnessed the selective and reversible ion binding features of ionophores to fabricate an ultrathin, ionophore-based K+-selective polyamide membrane through molecular layer-by-layer (m-LbL) polymerization with 18-crown-6-functionalized monomers. Compared with Cs+, Li+, and Mg2+, K+ exhibited the highest binding energy to 18-crown-6, facilitating its transport over the competing cations across the sub-10 nm polyamide film in a binary salt mixture. The need for competitive binding for selective K+ transport was further demonstrated through investigations of ion selectivity at varying concentration ratios between K+ and competing cations. Additionally, we extended the Nernst–Planck equation to describe individual ion flux in a binary system, identifying factors that govern ion transport. Our findings demonstrate the potential of selective single-ion transport enabled by preferential ion binding, showing promise for the development of biomimetic ion-selective polymeric membranes.