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.

中文翻译：

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仿生框架催化剂：从酶固定化到仿生催化

酶促催化由于其高效率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阻碍了酶的应用潜力。在化学转化实际需求的推动下，人们长期以来一直在寻求能够复制甚至超越天然酶功能的仿生催化剂。作为具有高表面积和结晶度的纳米多孔材料，金属有机框架 (MOF) 代表了天然酶及其活性位点如何整合到多孔固体中的一个绝妙案例，提供了具有卓越稳定性和可定制结构的仿生多相催化剂。在这篇综述中，我们全面总结了仿生 MOFs 在催化方面的进展，讨论了各种基于 MOF 的催化剂的设计原理，例如 MOF-酶复合材料和嵌入活性位点的 MOF，并探索这些催化剂在不同反应中的效用。与均相超分子催化剂相比，还强调了 MOF 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。