Developing monovalent cation permselective membranes (MCPMs) with high-efficient permselectivity is the core concern in specific industrial applications. In this work, we have fabricated a series of novel cation exchange membranes (CEMs) based on sulfonated polysulfone (SPSF) surface modification by polyethyleneimine (PEI) and 4′-aminobenzo-12-crown-4 (12C4) codeposited with dopamine (DA) successively, which was followed by the cross-linking of glutaraldehyde (GA). The as-prepared membranes before and after modification were systematically characterized with regard to their structures as well as their physicochemical and electrochemical properties. Particularly, the codeposition sequence of modified ingredients was investigated on galvanostatic permselectivity to cations. The modified membrane (M-12C4-0.50-PEI) exhibits significantly prominent selectivity to Li⁺ ions (${\mathrm{P}}_{{\mathrm{Mg}}^{2+}}^{{\mathrm{Li}}^{+}}$ = 5.23) and K⁺ ions (${\mathrm{P}}_{{\mathrm{Mg}}^{2+}}^{{\mathrm{K}}^{+}}$ = 13.56) in Li⁺/Mg²⁺ and K⁺/Mg²⁺ systems in electrodialysis (ED), which is far superior to the pristine membrane (M-0, ${\mathrm{P}}_{{\mathrm{Mg}}^{2+}}^{{\mathrm{Li}}^{+}}$ = 0.46, ${\mathrm{P}}_{{\mathrm{Mg}}^{2+}}^{{\mathrm{K}}^{+}}$ = 1.23) at a constant current density of 5.0 mA·cm⁻². It possibly arises from the synergistic effects of electrostatic repulsion (positively charged PEI), pore-size sieving (distribution of modified ingredients), and specific interaction effect (12C4 ~Li⁺). This facile strategy may provide new insights into developing selective CEMs in the separation of specific cations by ED.

A facile membrane surface modification process for improving permselectivity and antimicrobial property was proposed. A polydopamine (PDA) coating was firstly fabricated on pristine anion exchange membrane (AEM), followed by in situ reduction of Ag without adding any extra reductant. Finally, 2,5-diaminobenzene sulfonic acid (DSA) was grafted onto PDA layer via Michael addition reaction. The as-prepared AEM exhibited improved permselectivity (from 0.60 to 1.43) and effective inhibition of bacterial growth. In addition, the result of the long-term (90-h continuous electrodialysis) test expressed the excellent durability of the modified layer on membrane surface, because the concentration of Cl⁻ and SO₄²⁻ in diluted chamber fluctuated ~0.024 and 0.030 mol·L⁻¹ with no distinct decline. The method described in this work makes the full use of multifunctional PDA layer (polymer-like coating, in situ reduction and post-organic reaction), and a rational design of functional AEM was established for better practical application.

The industrial application of modified ion-exchange membranes is limited by complex, discontinuous ex-situ processes. This study introduces an in-situ electro-assembly strategy that enables the direct fabrication of a selective layer within an electrodialysis stack without disassembly. By utilizing a programmed current reversal to orchestrate the sequential deposition of polyethyleneimine (PEI), glutaraldehyde cross-linking, and polystyrene sulfonate (PSS) adsorption, we achieve meticulous interfacial engineering on a commercial cation exchange membrane. Comprehensive characterization confirms the successful construction of a hydrophilic, charge-tuned multilayer, which enhances ion transport kinetics and raises the limiting current density. This method culminates in a membrane with an exceptional Li⁺/Mg²⁺ selectivity of 107.9 and robust stability, retaining a significant selectivity of 47 over 10 cycles in real salt lake brine. This synergistic integration of operational simplicity, interfacial precision, and superior performance establishes a transformative and scalable platform for manufacturing high-performance membranes for selective ion separation from complex brine sources.