Mix-Charged Nanofiltration Membrane for Efficient Organic Removal from High-Salinity Wastewater: The Role of Charge Spatial Distribution.

The efficient removal of organic contaminants from high-salinity wastewater is crucial for resource recovery and achieving zero discharge. Nanofiltration (NF) membranes are effective in separating organic compounds and monovalent salts, but they typically exhibit an excessive rejection of divalent salts. Modifying the charge characteristics of NF membranes can improve salt permeation; however, the role of charge spatial distribution in governing salt transport behavior is not fully understood. In this study, we developed a mix-charged NF membrane with a horizontal charge distribution by employing interfacial polymerization combined with a polyester template etching and solvent-induced polyamine intercalation strategy. The ratio of positive to negative charge domains in the membrane can be precisely controlled by adjusting the aqueous monomer ratio and polyamine modifier type. X-ray photoelectron spectroscopy (XPS) depth profiling and separation layer thickness analysis confirmed the complete penetration of polyamines into the separation layer, providing direct evidence of the formation of horizontally distributed charge domains. This unique charge distribution results in a high charge density and a near-electroneutral surface, which facilitates the permeation of the divalent salts. The size-dependent "plug-in" modification and covalent cross-linking further reduce pore size, enhancing rejection of small organic molecules. Additionally, the membrane demonstrated exceptional antifouling performance against both negatively and positively charged pollutants, attributed to its unique charge distribution and smooth surface. Molecular dynamics (MD) simulations further revealed that weak electrostatic interactions and a tightly bound hydration layer contribute to the membrane's superior antifouling properties. This work provides valuable insights into the design of NF membranes with tailored microstructures and charge distributions for improved water treatment performance.