Metal–Organic Frameworks as a Versatile Materials Platform for Unlocking New Potentials in Biocatalysis

Abstract Biocatalysts immobilization with nanomaterials has promoted the development of biocatalysis significantly and made it an indispensable part of catalysis industries nowadays. Metal–organic frameworks (MOFs), constructed from organic linkers and metal ions or clusters, have raised significant interests for biocatalysts immobilization in recent years. The diversity of building units, molecular‐scale tunability, and modular synthetic routes of MOFs greatly expand its ability as the host to integrate with biocatalysts. In this review, the general synthetic strategies of MOFs with biocatalysts are first summarized. Then, the recent progress of MOFs as a versatile host for a series of biocatalysts, including natural enzymes, nanozymes, and organism‐based biocatalysts, followed by the introduction of MOFs themselves as biocatalysts, is discussed. Furthermore, the stimuli‐responsive properties of MOFs themselves or the additional functionalization of protein, polymer, and peptide within/on MOF that enable the biocatalysts with the controllable and tunable behavior are also summarized, which could unlock new potentials in biocatalysis. Finally, a perspective of the upcoming challenges, potential impacts, and future directions of biocatalytic MOFs is provided.