Hemin-Modified Multi-Walled Carbon Nanotube-Incorporated PVDF Membranes: Computational and Experimental Studies on Oil–Water Emulsion Separations

The separation of oil/water emulsions has attracted considerable attention for decades due to the negative environmental impacts brought by wastewater. Among the various membranes investigated for separation, polyvinylidene fluoride (PVDF) membranes have shown significant advantages of ease of fabrication, high selectivity, and fair pore distribution. However, PVDF membranes are hydrophobic and suffer from severe fouling resulting in substantial flux decline. Meanwhile, the incorporation of wettable substrates during fabrication has significantly impacted the membrane performance by lowering the fouling propensity. Herein, we report the fabrication of an iron-containing porphyrin (hemin)-modified multi-walled carbon nanotube incorporated PVDF membrane (HA-MWCNT) to enhance fouling resistance and the effective separation of oil-in-water emulsions. The fabricated membrane was thoroughly investigated using the FTIR, SEM, EDX, AFM, and contact angle (CA) analysis. The HA-MWCNT membrane exhibited a water CA of 62° ± 0.5 and excellent pure water permeance of 300.5 L/m(2)h at 3.0 bar (400% increment), in contrast to the pristine PVDF, which recorded a CA of 82° ± 0.8 and water permeance of 59.9 L/m(2)h. The hydrophilic HA-MWCNT membrane further showed an excellent oil rejection of >99% in the transmembrane pressure range of 0.5–2.5 bar and a superb flux recovery ratio (FRR) of 82%. Meanwhile, the classical molecular dynamics (MD) simulations revealed that the HA-MWCNT membrane had greater solvent-accessible pores, which enhanced water permeance while blocking the hydrocarbons. The incorporation of the hemin-modified MWCNT is thus an excellent strategy and could be adopted in the design of advanced membranes for oil/water separation.