Organic-Inorganic Co-Modified PVDF Membrane for High-Flux Oil/Water Separation and Simultaneous Multi-Pollutant Removal

The coexistence of emulsified oil, dissolved organics, and heavy metal ions in industrial oily wastewater makes one-step treatment highly challenging. Herein, an organic-inorganic co-modified PVDF composite membrane (MTSP) was fabricated via nonsolvent-induced phase separation, with tea polyphenols, SiO2, and fibrous MXene synergistically incorporated. The resulting membrane exhibited a superhydrophilic/underwater oleophobic surface, with a water contact angle of 1° and an underwater oil contact angle of ~136°, owing to the optimized surface chemistry and hierarchical pore structure. As a result, the MTSP membrane effectively suppressed oil fouling while enabling rapid water transport. At 0.1 bar, the optimized membrane delivered an oil/water separation efficiency of ~99.5% and a high flux of 2420–2670 L·m−2·h−1, while maintaining >99% separation efficiency for various emulsified oils, including kerosene, edible oil, n-hexane, and 1,2-dichloroethane. It also showed excellent recyclability and chemical stability, retaining >98–99% efficiency after five cycles and after 24 h exposure to pH 1 and pH 12 conditions. Notably, for complex simulated wastewater containing emulsified kerosene, phenol, and Fe3+, Cu2+, Zn2+, and Cd2+, the membrane maintained ~99% oil/water separation efficiency and simultaneously removed ~79% of phenol and 70–86% of heavy metal ions in a single filtration process. The superior performance is attributed to the synergistic effects of the superhydrophilic/underwater-oleophobic membrane surface, hierarchical transport channels enabling rapid water permeation, and multifunctional sites that adsorb/coordinate dissolved pollutants. This work provides a simple, scalable design strategy for PVDF-based membranes that integrate high-flux separation, antifouling performance, and multi-pollutant remediation for the treatment of complex oily wastewater.