Under-liquid dual superlyophobic nanofibrous polymer membranes achieved by coating thin-film composites: a design principle

Surfaces with under-liquid dual superlyophobicity have garnered tremendous interest because of their promising applications, but their unexplored underlying nature restricts the designed construction of such surfaces. Herein, we coated the thin-film composites with different terminal groups over the electrospun polyacrylonitrile nanofibrous membranes, which afforded the membranes excellent stability in organic solvents, as well as modulated under-liquid wetting behaviors. Among them, the representative under-liquid dual superlyophobic 4-cyan-Ph-terminated membrane could realize highly efficient separation of all types of oil/water mixtures and even emulsions. Moreover, we found that the under-liquid wetting behaviors could be classified in terms of the intrinsic water contact angle (θ(w)). By comparing the total interfacial energy, we proved that the under-liquid dual lyophobic surfaces were thermodynamically metastable. On this basis, we could predict the θ(w) of rough surfaces with the under-liquid dual lyophobicity in a given oil–water–solid system (e.g., 47.3–89.1° in cyclohexane–water–solid system, R = 2). This work provides a design principle for the fabrication of under-liquid dual superlyophobic surfaces, which will open potential applications in diverse fields in terms of such smart surfaces.