Enhanced monovalent selectivity of cation exchange membranes via adjustable charge density on functional layers

Electrodialysis (ED) technique is a typical and promising membrane process, for applications like water treatment and ion separation. Especially, the separation between monovalent and multivalent cations is a current central issue in many industries and academic researches. Herein, a series of novel cation exchange membranes were prepared from quaternized polyaniline modified sulfonated polyphenyl sulfone (SPPSU) by in-situ polymerization-deposited polyaniline followed by quaternizing with methyl iodide. Restricted divalent cation penetration and regulated monovalent cation transport were achieved by elevating the kinetic effect of electrostatic repulsion and narrowing water channel. Importantly, positive charge density of modification layer could be adjusted by controlling the degree of quaternization, which was accompanied by the change of water channel. When evaluated in a simulated mixed salt system (Mg2+/Na+ and Mg2+/Li+), the optimal quaternized polyaniline membrane exhibited a higher perm-selectivity (PNaMg=4.1, PLiMg=1.75) than initial polyaniline modified cation exchange membrane (PNaMg=0.8, PLiMg=0.75), and commercial monovalent-selective cations exchange membrane CIMS (PNaMg=3.56, PLiMg=1.11). This presented strategy is straightforward and effective, demonstrating the effect of surface positive charge layer on perm-selectivity.