Advances in the Preparation of Metal–Organic Framework-Derived Pyrolyzed Materials and Their Applications in Enzyme Immobilization

Abstract

Metal–organic framework (MOF)-derived pyrolytic materials retain the pristine MOF advantages—high porosity and large surface area—while offering markedly improved stability, making them promising enzyme immobilization carriers. Their pore sizes can be rationally tuned via prepyrolysis modification, in situ activation, or postpyrolysis treatment, thereby enabling the tailored immobilization of bulky enzymes such as lipases. This review is the first to systematically address the use of pyrolyzed MOFs for enzyme immobilization, filling a gap in the literature. We compare derivatives from N-containing, O-containing, and N/O-containing ligands, revealing that N/O-type ligands excel in accommodating large enzymes. Pyrolysis mechanisms under inert, oxidative, reducing, and H₂O atmospheres are summarized, linking each atmosphere to material properties. A dedicated section consolidates pore-enlargement strategies—a critical yet underexplored aspect. Finally, we demonstrate the potential of these materials to enhance enzyme stability, activity, and reusability in biocatalysis and biosensing, providing both a practical design guide and broader insights for catalysis, energy storage, and environmental applications.