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Study on the zinc porphyrins as potential carbonic anhydrase mimics for promoting CO2 absorption in K2CO3 solution

Yuchen Zhou,Zezhi Chen,Huijuan Gong,Xiaoshu Wang,Lu Chen,Huiqiang Yu

Zinc porphyrins, boasting a coordination environment akin to that of natural carbonic anhydrase (CA), coupled with excellent structural stability, built-in hydrophobic pocket, and suitable charge of center Zn 2+ , were considered as potential CA-mimics for CO 2 capture. To validate this assumption, three zinc porphyrin representatives, zinc porphin (ZnP), zinc protoporphyrin IX (ZnPP), and zinc meso -tetrakis(N-methylpyridinium-4-yl) porphyrin (ZnTMPyP), were prepared, and tested performance in enhancing CO 2 absorption in water and K 2 CO 3 solutions. The results from CO 2 absorption experiments indicated that ZnTMPyP with the optimal dosage increased CO 2 absorption rate by 44.25 % in water, and ZnPP with the optimal dosage increased the CO 2 absorption rate by 63.67 % in 20 wt% of K 2 CO 3 solution, which are respectively 1.53 and 2.07 times of CO 2 absorption performance of zinc cyclen (ZnC), the most effective CA-mimic reported. Besides, the zinc porphyrins demonstrated excellent stability and reusability throughout five cycles of CO 2 absorption and desorption, which are vital aspects for practical applications. Through the calorimetric method and density functional theory (DFT) calculations, it was confirmed that the prepared zinc porphyrins had similar enzymatic behavior and catalytic CO 2 hydration pathway to natural CA. According to the results of characterization and DFT calculations, high dispersion, the lowest charge of the Zn 2+ center, and the existence of additional CO 2 adsorption sites (propionate ions), endow ZnPP with the highest catalytic activity in the K 2 CO 3 solution.