Bioinspired Framework Catalysts: From Enzyme Immobilization to Biomimetic Catalysis

Abstract

Enzymatic catalysis has fueled considerable interest from chemists due to its high efficiency and selectivity. However, the structural complexity and vulnerability hamper the application potentials of enzymes. Driven by the practical demand for chemical conversion, there is a long-sought quest for bioinspired catalysts reproducing and even surpassing the functions of natural enzymes. As nanoporous materials with high surface areas and crystallinity, metal−organic frameworks (MOFs) represent an exquisite case of how natural enzymes and their active sites are integrated into porous solids, affording bioinspired heterogeneous catalysts with superior stability and customizable structures. In this review, we comprehensively summarize the advances of bioinspired MOFs for catalysis, discuss the design principle of various MOF-based catalysts, such as MOF−enzyme composites and MOFs embedded with active sites, and explore the utility of these catalysts in different reactions. The advantages of MOFs as enzyme mimetics are also highlighted, including confinement, templating effects, and functionality, in comparison with homogeneous supramolecular catalysts. A perspective is provided to discuss potential solutions addressing current challenges in MOF catalysis.

Structural and Functional Insights into the Biomineralized Zeolite Imidazole Frameworks

“…Such a reduction of reaction rate has also been discovered in the enzymes after encapsulation by ZIF-8 22,31 and other MOFs. 44 Despite the inhibition of the biocatalytic rate, the conversion efficiency, defined as the glucose conversion after 120 s, of GOx@ZIF-8 was comparable to that of the free GOx (Figure 2b). Yet, the conversion efficiency of GOx@ZIF-90 is only 8.86%, and ZIFzni showed almost no catalytic power.…”

Polypyridyl Ru(ii) or cyclometalated Ir(iii) functionalized architectures for photocatalysis

“…Furthermore, this MOF facilitated coupling reaction between the activated vinyl- or alkynyl-azaarenes and alkyl radicals. 167…”

“…14 3D Ru(N^N) 3 @(BPDCA+TAPM)-COF. Different from the polymeric networks of MOFs, COFs 167 and SOFs, metallasupramolecules are discrete architectures with sufficient solubility in solvents, that exhibit unique properties in solution, such as host-guest and liquid luminescence. 203,204 Like the synthesis of MOFs, the construction of metallasupramolecules is also based on the coordination-driven assembly of metal ions and ligands.…”

Self-Reconstructed Two-Dimensional Cluster-Based Co–Organic Layer Heterojunctions for Enhanced Oxygen Evolution Reactions

“…Metal–organic frameworks (MOFs), a family of porous materials formed by connecting metal nodes with organic ligands via coordination chemistry, have received special attention due to their flexible tunability (e.g., composition, structure, and morphology) and are considered one of the most promising materials for OER catalysts without precious metals. − Nevertheless, the intrinsic activity of MOF catalysts is greatly hindered by their weak mass/charge transfer capabilities. − In addition, the performance of catalytic materials is highly dependent on the bonding strength of key reactants at the surface active sites, and the bonding energies of OER-related intermediates (e.g., *O, *OH, and *OOH) are correlated with each other according to a linear scaling relationship, resulting in a “volcano diagram” type of performance map . To address these issues, the construction of heterojunction structures has emerged as one of the most effective approaches to enhance catalytic performance.…”