A Structural Mimic of Carbonic Anhydrase in Zeolitic Imidazolate Frameworks via Trans-functionalization for Enhancing Hydrolytic Activity

Metal-organic frameworks (MOFs) have been widely considered as ideal platforms for the preparation of biomimetic catalysts, but it remains challenging to fabricate MOF-based enzyme-like catalysts with optimal activity. Here, we leverage the inherent flexibility of MOFs and propose a novel trans-functionalization strategy to construct a carbonic anhydrase (CA) mimic by the structural transformation from ZIF-L to ZIF-8. Theoretical and experimental results reveal that during the structural transformation, the hydroxyl group will preferentially coordinate with the interlayer Zn clusters to form the CA-like active center Zn-N₃-OH. Therefore, more accessible active centers are generated on the as-prepared ZIF-8-OH, resulting in substantially enhanced catalytic activity in the hydrolysis of para-nitrophenyl acetate.