Planting Anion Channels in a Negatively Charged Polyamide Layer for Highly Selective Nanofiltration Separation

A nanofiltration (NF) membrane with high salt permeation and high retention of small organics is appealing for the treatment of high-salinity organic wastewater. However, the conventional negatively charged NF membranes commonly show high retention of divalent anions (e.g., SO4 2–), and the reported positively charged NF membranes normally suffer super low selectivity for small organics/Na2SO4 and high fouling potential. In this work, we propose a novel “etching–swelling–planting” strategy assisted by interfacial polymerization and mussel-inspired catecholamine chemistry to prepare a mix-charged NF membrane. By X-ray photoelectron spectroscopy depth profiling and pore size distribution analysis, it was found that such a strategy could not only deepen the positive charge distribution but also narrow the pore size. Molecular dynamics confirm that the planted polyethyleneimine chains play an important role to relay SO4 2– ions to facilitate their transport across the membrane, thus reversing the retention of Na2SO4 and glucose (43 vs 71%). Meanwhile, due to the high surface hydrophilicity and smoothness as well as the preservation of abundant negatively charged groups (−OH and −COOH) inside the separation layer, the obtained membrane exhibited excellent antifouling performance, even for the coking wastewater. This study advances the importance of vertical charge distribution of NF membranes in separation selectivity and antifouling performance.