Regulation of Ion Binding Sites in Covalent Organic Framework Membranes for Enhanced Selectivity under High Ionic Competition

The strategic spatial positioning of ion affinity sites within biological ion channels and their cooperative binding with the targeted ions are pivotal for enhancing ion recognition and ensuring exceptional selectivity in high ionic competition scenarios. However, the application of these principles to artificial ion channels remains largely unexplored. Herein, we present a series of covalent organic framework (COF) membranes, engineered with oxygen functional groups aligned along the rims of oriented COF pore channels of varying sizes to achieve a precise spatial arrangement of ion affinity sites. A notable COF membrane, featuring subnanometer pores decorated alternately with carbonyl and amide groups, demonstrated outstanding selectivity, achieving a Li/Mg selectivity ratio of 513 under equal mole and electrodialysis conditions. Impressively, as the Mg/Li ratio in the source solution increased to 16.6, the selectivity ratio rose to 833, significantly exceeding the reductions typically seen in conventional selective electrodialysis and nanofiltration methods. Both simulation and experimental analyses indicate that this exceptional selectivity stems from the cooperative binding between the oxygen functional groups and Li⁺ ions within the confined nanochannels, facilitating the preferential transport of Li⁺ ions. These findings provide a promising approach for designing selective ion extraction systems that function effectively in highly competitive environments.