Multienzyme Immobilization on PVDF Membrane via One-Step Mussel-Inspired Method: Enhancing Fouling Resistance and Self-Cleaning Efficiency

Immobilizing different enzymes on membranes can result in biocatalytic active membranes with a self-cleaning capacity toward a complex mixture of foulants. The membrane modification can reduce fouling and enhance filtration performance. Protease, lipase, and amylase were immobilized on poly(vinylidene fluoride) (PVDF) microfiltration membranes using a polydopamine coating in a one-step method. The concentrations of polydopamine precursor and enzymes were optimized during the immobilization. The higher hydrolytic activities were obtained using 0.2 mg/mL of dopamine hydrochloride and 4 mg/mL of enzymes: 0.90 mg_starch/min·cm² for amylase, 10.16 nmol_tyrosine/min·cm² for protease, and 20.48 µmol_{p-nitrophenol}/min·cm² for lipase. Filtration tests using a protein, lipid, and carbohydrate mixture showed that the modified membrane retained 41%, 29%, and 28% of its initial water permeance (1808 ± 39 L/m²·h·bar) after three consecutive filtration cycles, respectively. In contrast, the pristine membrane (initial water permeance of 2016 ± 40 L/m²·h·bar) retained only 23%, 12%, and 8%. Filtrations of milk powder solution were also performed to simulate dairy industry wastewater: the modified membrane maintained 28%, 26%, and 26% of its initial water permeance after three consecutive filtration cycles, respectively, and the pristine membrane retained 34%, 21%, and 7%. The modified membrane showed increased fouling resistance against a mixture of foulants and presented a similar water permeance after three cycles of simulated dairy wastewater filtration. Membrane fouling is reduced by the immobilized enzymes through two mechanisms: increased membrane hydrophilicity (evidenced by the reduced water contact angle after modification) and the enzymatic hydrolysis of foulants as they accumulate on the membrane surface.