Superhydrophobic PCTFE-based Microporous Membrane for Water/Oil Emulsion Separation in Various Environments

The separation of oil from oily water is a critical endeavor owing to the escalating global oil pollution. Membrane separation technology has gained widespread adoption for oily water treatment. Inspired by the vertical segregation phenomenon in drying multi-component suspensions, this study proposed an evaporation-induced stratification coupled with sacrificial template method to prepare superhydrophobic polychlorotrifluoroethylene (PCTFE) membrane for fast gravity-driven oil/water separation. The precursor of PCTFE microporous membranes, PCTFE/fluoroelastomer/hydrophobic silica nanoparticles (PCTFE/FR/SiO2) composite films, were fabricated via a solvent-assisted method. Induced by solvent evaporation, the pre-fabricated composite films exhibited a stratified structure, where SiO2 nanoparticles enriched near the top surfaces, making it easily tailor the surficial wettability. For the matrix, PCTFE-rich domains and FR-rich domains intersected, forming a bicontinuous structure. After sacrificing FR, PCTFE porous membranes were obtained. Meanwhile, the PCTFE-based porous skeletons combining with surface enriched SiO2 nanoparticles constructed a multi-level roughness, thus achieving superhydrophobicity. The optimized membrane possessed an average pore size of ∼1.84 μm, a porosity of ∼60%, and a WCA above 155°, owning excellent self-cleaning properties and efficient oil/water separation ability. The membrane exhibited remarkable capability in various oil/water mixtures, including emulsified water-in-oil. The separation flux and oil recovery purity for water-in-dichloromethane emulsion were up to 2843±84 L/(m2·h) and 99.95 wt%, respectively. Furthermore, though being immersed into various organic solvents for 7 days or experiencing 15 separation cycles, the performances of the membranes hardly changed. Accordingly, this work provides a practical approach for tailoring surficial wettability and fabricating PCTFE-based membranes suitable for oil/water separation fields.