Stability of layer-by-layer nanofiltration membranes in highly saline streams

Layer-by-layer (LBL) assembly is an essential method for the preparation of nanofiltration (NF) membranes, offering tunable charge and pore size, high water permeability, and good anti-fouling properties, making them highly suitable for resource recovery, seawater desalination, and other fields. Despite their advantages, LBL NF membranes suffer from salinity instability, limiting their use in highly saline streams. This perspective review provides a summary of the fundamental physical and chemical principles of LBL assembly related to the salinity stability of LBL NF membranes. We critically analyze the driving force of LBL assembly, the binding strength of polyelectrolyte (PE) pairs, and the overcompensation of LBL membranes. We also discuss the factors affecting overcompensation level with respect to two different time scales. Furthermore, we examine the relationship between overcompensation level and salinity stability of LBL membranes, considering physical (osmotic pressure) and chemical (Le Chatelier's principle) aspects. Our analysis demonstrates that the salinity stability of LBL NF membranes in highly saline solutions can be improved by selecting PEs with stronger binding strength, increasing the overcompensation level, and chemical crosslinking. These methods not only enhance the salinity stability of LBL NF membranes but also offer greater potential for their future application in highly saline streams.