Climate change and the energy crisis, driven by excessive CO₂ emissions, have emerged as pressing global challenges. The conversion of CO₂ into high-value chemicals not only mitigates atmospheric CO₂ levels but also optimizes carbon resource utilization. Enzyme-catalyzed carbon technology offers a green and efficient approach to CO₂ conversion. However, free enzymes are prone to inactivation and denaturation under reaction conditions, which limit their practical applications. Metal–organic frameworks (MOFs) serve as effective carriers for enzyme immobilization, offering porous crystalline structures that enhance enzyme stability. Moreover, their high specific surface area facilitates strong gas adsorption, making enzyme@MOF composites particularly advantageous for CO₂ catalytic conversion. In this paper, we review the synthesis technologies and the application of enzyme@MOFs in CO₂ catalytic conversion. Furthermore, the strategies, including the enhancement of CO₂ utilization, coenzyme regeneration efficiency, and substrate mass transfer efficiency, are also discussed to further improve the efficiency of enzyme@MOFs in CO₂ conversion. The aim of this review is to present innovative ideas for future research and to highlight the potential applications of enzyme@MOFs in achieving efficient CO₂ conversion.

Oxidoreductases are a wide class of enzymes that can catalyze biological oxidation and reduction reactions. Nowadays, oxidoreductases play a vital part in most bioenergetic metabolic pathways, which have important applications in biodegradation, bioremediation, environmental applications, as well as biosensors. However, free oxidoreductases are not stable and hard to be recycled. In addition, cofactors are needed in most oxidoreductases catalyze reactions, which are so expensive and unstable that it hinders their industrial applications. Enzyme immobilization is a feasible strategy that can overcome these problems. Recently, metal–organic frameworks (MOFs) have shown great potential as support materials for immobilizing enzymes due to their unique properties, such as high surface-area-to-volume ratio, chemical stability, functional designability, and tunable pore size. This review discussed the application of MOFs and their composites as immobilized carriers of oxidoreductase, as well as the application of MOFs as catalysts and immobilized carriers in redox reactions in the perspective of the function of MOFs materials. The paper also focuses on the potential of MOF carrier-based oxidoreductase immobilization for designing an enzyme cascade reaction system.

Chiral metal–organic frameworks (cMOFs) are emerging chiral stationary phases for enantioseparation owing to their porosity and designability. However, a great number of cMOF materials show poor separation performance for chiral drugs in high-performance liquid chromatography (HPLC). The possible reasons might be the irregular shapes of MOFs and the low grafting degree of chiral ligands. Herein, MIL−101−Ppa@SiO₂ was synthesized by a simple coordination post-synthetic modification method using (S)-(+)-2-Phenylpropionic acid and applied as the chiral stationary phase to separate chiral compounds by HPLC. NH₂−MIL−101−Ppa@SiO₂ prepared via covalent post-synthetic modification was used for comparison. The results showed that the chiral ligand density of MIL−101−Ppa@SiO₂ was higher than that of NH₂−MIL−101−Ppa@SiO₂, and the MIL−101−Ppa@SiO₂ column exhibited better chiral separation performance and structural stability. The binding affinities between MIL−101−Ppa@SiO₂ and chiral compounds were simulated to prove the mechanism of the molecular interactions during HPLC. These results revealed that cMOFs prepared by coordination post-synthetic modification could increase the grafting degree and enhance the separation performance. This method can provide ideas for the synthesis of cMOFs.