Ultrathin polyamide nanofilms are desirable as the separation layers for the highly permeable thin-film composite (TFC) membranes, and recently, their lowest thickness limits have attracted a lot of attention from researchers. Due to the interference of the underlying substrate, preparing a defect-free, ultrathin polyamide nanofilm directly on top of a membrane substrate remains a great challenge. Herein, we report a novel fabrication technique of TFC membranes, named in situ free interfacial polymerization (IFIP), where the IP reaction occurs at the uniform, free oil-water interface dozens of microns above the substrate, and then the resulting nanofilm spontaneously assembles into the TFC structure without extra manual transfer. This IFIP method not only overcomes the limitations of conventional IP, succeeding in preparing ultrathin-nanofilm composite membranes for nanofiltration and reverse osmosis application, but also enables scale membrane manufacturing that is not feasible via previously reported free-standing IP. Based on the IFIP method, the thickness of the polyamide nanofilm was successfully reduced to ca. 3-4 nm, which we believe is close to the ultrathin limit of the polyamide nanofilm for separation application. Meanwhile, the structure-performance relationship revealed that the strategy of increasing TFC membrane permeance by reducing polyamide layer thickness also had a limit. Besides, the IP mechanisms in regard to the formation of surface morphology and film growth were explored by combining experimental and molecular simulation methods. Overall, this work is expected to push forward the fundamental study and practical application of the ultrathin-film composite membrane.
Keywords: composite membranes; desalination; interfacial polymerization; nanofiltration; reverse osmosis; ultrathin polyamide films.