Engineering Zinc–Organic Frameworks‐Based Artificial Carbonic Anhydrase with Ultrafast Biomimetic Centers for Efficient Hydration Reactions

Abstract Constructing effective and robust biocatalysts with carbonic anhydrase (CA)‐mimetic activities offers an alternative and promising pathway for diverse CO 2 ‐related catalytic applications. However, there is very limited success has been achieved in controllably synthesizing CA‐mimetic biocatalysts. Here, inspired by the 3D coordination environments of CAs, this study reports on the design of an ultrafast ZnN 3 ‐OH 2 center via tuning the 3D coordination structures and mesoporous defects in a zinc–dipyrazolate framework to serve as new, efficient, and robust CA‐mimetic biocatalysts (CABs) to catalyze the hydration reactions. Owing to the structural advantages and high similarity with the active center of natural CAs, the double‐walled CAB with mesoporous defects displays superior CA‐like reaction kinetics in p ‐NPA hydrolysis ( V 0 = 445.16 nM s −1 , V max = 3.83 µM s −1 , turnover number: 5.97 × 10 −3 s −1 ), which surpasses the by‐far‐reported metal–organic frameworks‐based biocatalysts. This work offers essential guidance in tuning 3D coordination environments in artificial enzymes and proposes a new strategy to create high‐performance CA‐mimetic biocatalysts for broad applications, such as CO 2 hydration/capture, CO 2 sensing, and abundant hydrolytic reactions.