Abstract
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.
Highlights
Catalysis occupies a pivotal role in the modernization of our chemical industry, because it ensures more efficient use of natural resources and aids in the minimization of waste production
This review aims to illustrate the influence of confinement on the selectivity and activity in catalysis, by highlighting relevant studies in both heterogeneous and homogeneous catalysis
One of the essential elements is the specific cage around the active site, which in enzymes is defined by the peptide environment
Summary
Catalysis occupies a pivotal role in the modernization of our chemical industry, because it ensures more efficient use of natural resources and aids in the minimization of waste production. An essential aspect in this context is the preservation of a well-defined confined space (second coordination sphere) around the active center, for a number of reasons It ensures proximity of substrate(s) and the catalyst active site, thereby enhancing overall reaction rates by just pre-organization. The cage can destabilize intermediates to lower the transition state barriers (Alber et al, 1983) These effects describe in general terms how the second coordination sphere surrounding the active site of an enzyme contributes to enhanced catalyst performance. Relevant studies will be put into context with the aim to provide fundamental understandings on how confinement effects can influence selectivity and activity in catalysis
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