Hypersaline wastewater treatment using membrane distillation (MD) has gained significant attention due to its ability to completely reject nonvolatile substances. However, a critical limitation of current MD membranes is their inability to intercept volatile substances owing to their large membrane pores. Additionally, the strong interaction between volatile substances and MD membranes underwater tends to cause membrane wetting. To overcome these challenges, we developed a dual-layer thin film composite (TFC) Janus membrane through electrospinning and sequential interfacial polymerization of a polyamide (PA) layer and cross-linking a polyvinyl alcohol/polyacrylic acid (PP) layer. The resulting Janus membrane exhibited high flux (>27 L m–2 h–1), salt rejection of ∼100%, phenol rejection of ∼90%, and excellent resistance to wetting and fouling. The interlayered interface between the PA and PP layer allowed the sieve of volatile substances by limiting their dissolution–diffusion, with the increasing hydrogen bond network formation preventing their transport. In contrast, small water molecules with powerful dynamics were permeable through the TFC membrane. Both experimental and molecular dynamics simulation results elucidated the sieving mechanism. Our findings demonstrate that this type of TFC Janus membrane can serve as a novel strategy to design next-generation MD membranes against volatile and non-volatile contaminants, which can have significant implications in the treatment of complex hypersaline wastewater.

Membrane distillation holds promise for further recovery of reverse osmosis (RO)-concentrated seawater to realize zero-liquid discharge; however, severe scaling induced by high-concentration salts and fouling triggered by a naturally occurring substance would result in severe wetting of the hydrophobic distillation membrane. To retard membrane wetting during the concentration process, the membrane’s interfacial structure and the seawater’s ingredients were systematically investigated to improve the membrane’s durability. The results demonstrated that the dual-layer membrane with hierarchically rough beads-on-a-string structured fibers could enlarge the water evaporation area on the membrane surface to improve membrane water flux, and superhydrophobicity can reduce the contact area between the salt and membrane surface to prevent membrane scaling. Significantly, the membrane’s durability can be further improved by adjusting the seawater ingredients. This finding revealed that the scaling resulting from Ca2+ and Mg2+ when they exist alone is more severe than when they exist together. Therefore, eliminating the dominant Ca2+, Mg2+, and naturally occurring substance in seawater and maintaining it in a neutral state can stably concentrate the seawater with a high water recovery of ∼85%. The regulation of the membrane interface integrated with optimal seawater ingredients is essential for the application of membrane distillation in the treatment of RO-concentrated seawater.