Mouarrawis Valentinos, Plessius Raoul, van der Vlugt Jarl Ivar, Reek Joost N H
Homogeneous, Supramolecular and Bio-Inspired Catalysis (HomKat) Group, Van 't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Amsterdam, Netherlands.
Front Chem. 2018 Dec 21;6:623. doi: 10.3389/fchem.2018.00623. eCollection 2018.
This review focuses on the effects that confinement of molecular and heterogeneous catalysts with well-defined structure has on the selectivity and activity of these systems. A general introduction about catalysis and how the working principles of enzymes can be used as a source of inspiration for the preparation of catalysts with enhanced performance is provided. Subsequently, relevant studies demonstrate the importance of second coordination sphere effects in a broad sense (in homogeneous and heterogeneous catalysis). Firstly, we discuss examples involving zeolites, MOFs and COFs as heterogeneous catalysts with well-defined structures where confinement influences catalytic performance. Then, specific cases of homogeneous catalysts where non-covalent interactions determine the selectivity and activity are treated in detail. This includes examples based on cyclodextrins, calix[n]arenes, cucurbit[n]urils, and self-assembled container molecules. Throughout the review, the impact of confined spaces is emphasized and put into context, in order to get a better understanding of the effects of confinement on catalyst performance. In addition, this analysis intends to showcase the similarities between homogeneous and heterogeneous catalysts, which may aid the development of novel strategies.
本综述聚焦于具有明确结构的分子催化剂和多相催化剂的限域作用对这些体系的选择性和活性的影响。文中提供了关于催化的一般性介绍，以及酶的工作原理如何能够作为制备具有更高性能催化剂的灵感来源。随后，相关研究证明了广义上第二配位层效应（在均相和多相催化中）的重要性。首先，我们讨论涉及沸石、金属有机框架材料（MOFs）和共价有机框架材料（COFs）作为具有明确结构的多相催化剂的例子，其中限域作用会影响催化性能。然后，详细探讨了非共价相互作用决定选择性和活性的均相催化剂的具体案例。这包括基于环糊精、杯[n]芳烃、葫芦[n]脲和自组装容器分子的例子。在整个综述中，强调并结合实际情况阐述了限域空间的影响，以便更好地理解限域对催化剂性能的作用。此外，该分析旨在展示均相催化剂和多相催化剂之间的相似性，这可能有助于开发新的策略。
