Photocatalytic PAN Nanofibrous Membrane through Anchoring a Nanoflower-Branched CoAl-LDH@PANI Heterojunction for Organic Hazards Degradation and Oil-Containing Emulsified Wastewater Separation.

The synergistic treatment of oily wastewater containing organic hazards and emulsified oils remains a big challenge for membrane separation technology. Herein, the photocatalytic membrane, which combined the physical barrier and catalytic oxidation-driven degradation functionality, was fabricated via anchoring a nanoflower-branched CoAl-LDH@PANI Z-scheme heterojunction onto a porous polyacrylonitrile mat and using tannic acid as an adhesive. The assembly of such a Z-scheme heterojunction offered the superior photocatalytic degradation performance of soluble dyes and tetracycline (up to 94.3%) to the membrane with the improved photocatalytic activity of 2.33 times compared with the CoAl-LDH@pPAN membrane. Quenching experiments suggested that the •O2- was the most reactive oxygen species in the catalytic reaction system of the composite membrane. The greatly enhanced photocatalytic activity was attributed to the effective inhibition of photogenerated hole-electron combination using PANI as a carrier, with charge transferring from LDH to PANI. The possible photocatalytic degradation mechanism was proposed based on VB-XPS, electron spin resonance spectroscopy, and DRS technologies, which was confirmed by density functional theory calculation. Meanwhile, benefiting from the superhydrophilic/oleophobic feature and low oil adhesion, the membrane exhibited high permeability for isooctane emulsion (3990.39 L·m-2·h-1), high structure stability, and satisfactory cycling performance. This work provided a strategy to develop superwetting and photocatalytic composite membranes for treating complex multicomponent pollutants in the chemical industry.

Design and assembly of Ag-decorated Bi2O3 @ 3D MXene Schottky heterojunction for the highly permeable and multiple-antifouling of fibrous membrane in the purification of complex emulsified oil pollutants.

Membrane separation technology has potential for purifying emulsified oily wastewater. However, the oils, soluble organic substances, and microorganisms can cause complex membrane fouling problems, thereby reducing the separation efficiency and service life. Herein, a highly permeable and multiple-antifouling composite membrane was prepared using porous PAN fibrous mat as support backbone for the assembly of Ag-decorated Bi2O3 @ 3D MXene Schottky heterojunction and hydrophilic TA as the adhesive. The unique arrangement of 3D MXene heterojunction and hydrophilic functionalization effectively broke through the limitation of separation flux and synergistically enhanced the anti-fouling performance of membrane. Such fibrous composite membrane achieved an exceedingly high permeability (2717-3328 L·m-2·h-1) for various emulsified oils, while ensuring excellent oil/water emulsion retention rate (99.59%) and good cycle stability. Meanwhile, the composite membrane displayed favorable photocatalytic degradation performance toward degrading MeB (96.1%) and antibacterial ability. Furthermore, the MD simulation and free radical trapping experiments were carried out to unravel the molecular interactions during the separation process and the photocatalytic mechanism of composite membrane, respectively. Overall, the combination of photocatalytic self-cleaning, anti-oil adhesion, and antibacterial effect renders the membrane high permeability and multiple-antifouling performance, which provides a new strategy for dealing with complex oily wastewater in petrochemical industry.