Cation-permselective membranes enabled by synergistic ion channels of crown ethers and anionic sites

The specific interaction existing between crown ethers (CEs) and alkali metal ions serves a dual purpose in both facilitating the selective ion transport across polymeric membranes and exerting a significant influence on the microstructure by means of non-covalent interactions among the CEs. In this study, synergistic ion channels featuring a bi-periodic structure are constructed using both CEs and sulfonate (−SO3−) groups. It is observed that the membranes with reduced water uptake demonstrate enhanced ion permselectivity, attributable to the partial dehydration of ions during binding behavior. The bi-functional membranes exhibit excellent permselectivity for alkali metal ions, particularly K+, Na+ and Li+ ions, over Mg2+ ions. The permselectivity sequence of K+>Na+>Li+ and the notably superior K+/Mg2+ permselectivity, reaching up to 244.43, is attributed to the relatively stable CE-K+ complex within the channels, as supported by molecular dynamics simulations. Specifically, the fabricated membrane is successfully utilized in a 4-stage "ion-distillation" process, achieving an impressive separation factor for K+/Mg2+ over 40,000. The investigation of the synergy between CEs and anionic sites provides valuable insights for the development of cation-permselective membranes.