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Water resources have been significantly affected by the growth of the modern industry as well as regular marine oil spills, which has led people to develop cutting-edge technology or materials for the treatment of oily wastewater. Herein, we successfully decorated the surface of the electrospun nanofibrous (NF) PVDF membrane with a photocatalytic TiO2 nano cauliflower-like structure with a facile, cost-effective hydrothermal approach. Taking advantage of the surface’s micro/nano structure, the NF TiO2@PVDF nano cauliflower-like membrane shows magnificent surface wettability, photocatalytic degradability, and robustness. It can separate both water-in-oil mixture and surfactant-stabilized water-in-oil emulsions with a high degree of separation efficiency because of the wetting behavior of the membrane. Moreover, taking advantage of the photocatalytic nature of the TiO2, the resultant NF TiO2@PVDF nano cauliflower-like membrane can also be used in degrading pharmaceutical and organic pollutants to address wastewater treatment. Given the distinctive supremacy of the aforementioned modified NF PVDF membrane, the technique can encourage the widespread development of multifunctional superwetting materials presenting an appealing potential for complex oily wastewater treatment.

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