Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071, China.
Chem Rev. 2023 May 10;123(9):5347-5420. doi: 10.1021/acs.chemrev.2c00879. Epub 2023 Apr 12.
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.
酶催化因其高效性和选择性而引起了化学家的极大兴趣。然而，结构的复杂性和脆弱性限制了酶的应用潜力。受化学转化实际需求的驱动，人们一直在寻求能够复制甚至超越天然酶功能的仿生催化剂。金属-有机骨架（MOFs）作为具有高表面积和结晶度的纳米多孔材料，代表了一种将天然酶及其活性位点整合到多孔固体中的精巧范例，为具有优越稳定性和可定制结构的仿生异相催化剂提供了可能。在这篇综述中，我们全面总结了用于催化的仿生 MOFs 的进展，讨论了各种基于 MOF 的催化剂（如 MOF-酶复合材料和嵌入活性位点的 MOFs）的设计原理，并探讨了这些催化剂在不同反应中的应用。还比较了同相超分子催化剂，突出了 MOFs 作为酶模拟物的优势，包括限制、模板效应和功能。提供了一个视角来讨论解决 MOF 催化中当前挑战的潜在解决方案。
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