Synergistic integration of surface patterning and multi-component modification in PVDF membranes for efficient oily wastewater treatment

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Emulsified oily wastewater is difficult to treat because of its complex composition and high stability. This study developed a modified polyvinylidene fluoride (PVDF) membrane by integrating microcrystalline cellulose (MCC), tannic acid (TA), polydopamine (PDA), and controlled surface patterning, thereby combining multi-component chemical functionalization with hierarchical surface structuring. The membrane was fabricated by non-solvent-induced phase separation, surface embossing, MCC modification and regeneration, TA deposition, and PDA self-polymerization. The optimized D4 membrane, prepared with 3% MCC, 1% TA, 6 h PDA polymerization, and a 20 μm imprinting depth, reduced the water contact angle from 81.7° to 44.0° and increased porosity from 67.32% to 82.67%. For edible-oil, engine-oil, and diesel-oil emulsions, D4 achieved fluxes of 170.24, 210.83, and 223.91 L·m⁻²·h⁻¹ with rejection efficiencies of 94.73%, 98.03%, and 95.63%, respectively. In BSA fouling tests, FRR, Rt, Rr, and Rir were 89.6%, 40.3%, 29.9%, and 10.4%, respectively. The improved performance was associated with enhanced hydrophilicity and the SEM-observed peak–valley structure, supporting improved wetting, mass transfer, and fouling reversibility.

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