Immobilization of carbonic anhydrase on polyvinylidene fluoride membranes

In recent years, the application of carbonic anhydrase (CA) in CO₂ removal has attracted great interest. However, obtaining high enzyme recovery activity is difficult in existing immobilization techniques. In this work, water plasma–treated poly(vinylidene fluoride) (PVDF) membranes were modified via 3-aminopropyl triethoxy silane (KH550) or γ-(2, 3-epoxypropoxy) propyl trimethoxy silane (KH560), and then CA was attached. The immobilization process was optimized, and the catalytic properties of PVDF-attached CA were characterized. The maximum activity recovery of PVDF-KH550-CA was 60%, whereas that of PVDF-KH560-CA was 33%. The K_m values of PVDF-KH550-CA, PVDF-KH560-CA, and free enzyme were 9.97 ± 0.37, 12.5 ± 0.2, and 6.18 ± 0.23 mM, respectively, and their K_cat/K_m values were 206 ± 2, 117 ± 5, and 488 ± 4 M⁻¹·Sec⁻¹. PVDF-attached CA shows excellent storage stability and reusability, and their half-life values were 82 and 78 days at 4 °C. At 25 °C, they were 50 and 37 days, respectively. PVDF-KH550-CA and PVDF-KH560-CA retained approximately 85% and 72% of the initial activity after undergoing 10 cycles. In the presence of them, the generation rates of CaCO₃ were 76% and 65% of the free CA system, which were 1.6 and 1.3 times that of the blank system, respectively. Its role in accelerating CO₂ sequestration holds great promise for its practical application.