Polyphenol assisted assembly of prussian blue analogs nanocrystals decorated 3D GO functional microspheres for polymer fiber bifunctional membrane with high oil-water emulsion permeability and powerful photocatalytic self-cleaning ability

Due to the intricate components of wastewater and physical stacking of graphene oxide (GO), the current GO membranes exhibit the fatal defects of low porosity and poor anti-fouling ability. Herein, a three dimensional (3D) FeCo-PBA@GO functional microsphere was constructed via anchoring GO nanosheets onto hard template of 3D polymethyl methacrylate (PMMA) microsphere driven by hydrogen bond and van der Waals force. On this basis, the Prussian blue analogs nanocrystals (FeCo-PBA) grew in situ on such functional microsphere and further assembled onto porous polyacrylonitrile (PAN) fiber mat through the tannic acid assisted spraying technique, resulting in highly permeable and photocatalytic self-cleaning FeCo-PBA@GO/PAN fibrous composite membrane. Interestingly, the unique 3D nanostructure of FeCo-PBA@GO microsphere arranging on membrane surface effectively prevented the dense physical stacking of GO nanosheets and increased the oil repellence property, thereby regulating the water channel and breaking through permeability limitation of membrane. As a result, the composite membrane exhibited superior separation fluxes (˃3029 L m −2 h −1 ) for different oil/water (O/W) emulsions, with rejection rate above 99.0 %. Owing to rich active sites and enhanced electron/mass transport property of FeCo-PBA functional layer, the composite membrane could effectively degrade various dyes by peroxymonosulfate (PMS) activation, with the degradation efficiency of 93.1–96.9 % within 40 min and demonstrated favorable antifouling and photocatalytic self-cleaning ability after cycling separation of O/W emulsion. In addition, the generated multiple reactive oxygen species and photocatalytic mechanism were proposed. This work provides a versatile pathway to prepare multifunctional GO advanced membranes for large-scale treatment of complex emulsified oily wastewater. • The bifunctional PAN fibrous composite membrane was prepared. • 3D FeCo-PBA@GO functionalized microsphere was designed as skin layer of membrane. • Membrane showed superior permeability compared to traditional GO lamellar membrane. • Membrane achieved photocatalytic self-cleaning and ultra-low oil adhesion.