In the practical purification of oily wastewater, the application of polymer-based membrane is greatly restricted due to the oil adhesion and complicated fouling problems. Herein, to conquer the aforementioned challenges, we prepared the polyphenol mediated Photo-Fenton self-cleaning and superhydrophilic/underwater superoleophobic α-FeOOH/g-C3N4@PVDF composite membrane via simple vacuum-assisted self-assembly technology. The g-C3N4 nanosheets modified by tannic acid were introduced into the surface of PVDF ultrafiltration membrane, in which the intercalation structure was regulated by the random interpenetration of α-FeOOH nanorods. The abundant hydroxyl and amino groups and the rough micro-nano structure formed by intercalation structure were favorable for the superhydrophilic feature (WCA = 0°, UOCA>150°), thus resulting in ultra-low oil adhesion. Specially, the intercalation structure improved the water permeation channel, further promoting the water/oil separation flux. Therefore, the composite membrane exhibited superior separation flux (452.35–650.21 L m−2 h−1) and separation efficiency (>99.06 %) for various surfactant-stabilized emulsions. Moreover, thanks to the Photo-Fenton reaction, the composite membrane showed excellent degradation efficiency on simulated pollutants (various dyes) within 60 min (MeB: 95.55 %, CR: 90.83 %, MO: 98.90 %, CV: 95.11 %), showing satisfactory photocatalytic self-cleaning performance. This work provides a strategy for the potential application of polymer-based membranes in the treatment of complex surfactant-stabilized emulsion wastewater from petrochemical industry.
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