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Abstract Membrane consisting of ordered sub-nanochannels has been pursued in ion separation technology to achieve applications including desalination, environment management, and energy conversion. However, high-precision ion separation has not yet been achieved owing to the lack of deep understanding of ion transport mechanism in confined environments. Biological ion channels can conduct ions with ultrahigh permeability and selectivity, which is inseparable from the important role of channel size and “ion-channel” interaction. Here, inspired by the biological systems, we report the high-precision separation of monovalent and divalent cations in functionalized metal-organic framework (MOF) membranes (UiO-66-(X)2, X = NH2, SH, OH and OCH3). We find that the functional group (X) and size of the MOF sub-nanochannel synergistically regulate the ion binding affinity and dehydration process, which is the key in enlarging the transport activation energy difference between target and interference ions to improve the separation performance. The K+/Mg2+ selectivity of the UiO-66-(OCH3)2 membrane reaches as high as 1567.8. This work provides a gateway to the understanding of ion transport mechanism and development of high-precision ion separation membranes.

ABSTRACTTwo-dimensional (2D) covalent organic framework (COF) membranes featuring well-aligned and programmable vertical nanochannels have emerged as a promising candidate for advanced nanofluidic devices and showcased vast potential in the fields of smart-gating, ion-separation, and energy-harvesting. However, the transverse interlayer nanochannels with a height of sub-nanometer-scale in 2D-COF membranes have scarcely been studied in comparison. Here, we report the ion transport characteristics in 2D interlayer nanochannels of protonated COF membranes. The distinct surface-charge-governed ionic conductance in domination of electrolyte concentration below 10−3 M as well as the exceptional anion/cation (Cl−/K+) selectivity is revealed due to the pronounced charge and nano-confinement effects. Additionally, evident ion current rectification is witnessed when incorporating asymmetric geometry into the system, which is attributed to the dynamic process of ion enrichment and dissipation within the protonated nanochannels. This work offers immense prospects for 2D-COF membranes in the fields of biomimetic nanofluidic devices and cutting-edge electronic devices.