Hierarchically Structured CA@ZIF-8 Biohybrids for Carbon Dioxide Mineralization

Abstract

Carbonic anhydrase (CA) is a powerful biocatalyst for carbon dioxide (CO₂) mineralization, of which immobilization is usually used for maintaining its catalytic activity against harsh external stimuli. However, the incorporated materials for CA immobilization would commonly increase the internal diffusion resistance during the catalytic process, thereby decreasing the catalytic efficiency. In our study, poly-L-glutamic acid (PLGA) as the structure regulator was used to induce the synthesis of CA@zeolitic imidazolate framework-8 (CA@ZIF-8) biohybrids. The introduction of PLGA that could coordinate with Zn²⁺ interfered the crystallization of ZIF-8, thereby changing the morphological structure of CA@ZIF-8 biohybrids. With the increase of PLGA amount from 0 to 60 mg, PLGA(x)-CA@ZIF-8 biohybrids were gradually transformed from a dodecahedron structure to a 3D lamellar nano-flower structure, which caused elevated exposed surface area. Accordingly, the loading ratio was increased from 34.6 to 49.8 mg g_cat^-1, while the catalytic activity was elevated from 20.6 to 23.4%. The CO₂ conversion rate was enhanced by nearly two folds compared to PLGA(0)-CA@ZIF-8 under the optimized condition. The final CaCO₃ yield could reach 5.6 mg mg_cat^-1, whereas the reaction system could remain above 80% of the initial reaction activity after 8 cycles.

Keywords: Carbon dioxide mineralization; Carbonic anhydrase; Enzyme immobilization; Hierarchical structures; Metal–organic frameworks.