Demystifying the Role of Surfactant in Tailoring Polyamide Morphology for Enhanced Reverse Osmosis Performance: Mechanistic Insights and Environmental Implications.

Surfactant-assisted interfacial polymerization (IP) has shown strong potential to improve the separation performance of thin film composite polyamide membranes. A common belief is that the enhanced performance is attributed to accelerated amine diffusion induced by the surfactant, which can promote the IP reaction. However, we show enhanced membrane performance for Tween 80 (a common surfactant), even though it decreased the amine diffusion. Indeed, the membrane performance is closely related to its polyamide roughness features with numerous nanovoids. Inspired by the nanofoaming theory that relates the roughness features to nanobubbles degassed during the IP reaction, we hypothesize that the surfactant can stabilize the generated nanobubbles to tailor the formation of nanovoids. Accordingly, we obtained enlarged nanovoids when the surfactant was added below its critical micelle concentration (CMC). In addition, both the membrane permeance and selectivity were enhanced, thanks to the enlarged nanovoids and reduced defects in the polyamide layer. Increasing the concentration above CMC resulted in shrunken nanovoids and deteriorated performance, which can be ascribed to the decreased stabilization effect caused by micelle formation. Interestingly, better antifouling performance was also observed for the surfactant-assisted membranes. Our current study provides mechanistic insights into the critical role of surfactant during the IP reaction, which may have important implications for more efficient membrane-based desalination and water reuse.