Dynamic Interconversion of Metal Active Site Ensembles in Zeolite Catalysis
| Autor: | Casey B. Jones, Rajamani Gounder, Siddarth H. Krishna |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
biology
010405 organic chemistry Renewable Energy Sustainability and the Environment Chemistry General Chemical Engineering Active site General Chemistry 010402 general chemistry Heterogeneous catalysis 01 natural sciences Catalysis 0104 chemical sciences Metal Metals Computational chemistry Catalytic Domain visual_art Zeolites biology.protein visual_art.visual_art_medium Reactivity (chemistry) Zeolite |
| Zdroj: | Annual Review of Chemical and Biomolecular Engineering. 12:115-136 |
| ISSN: | 1947-5446 1947-5438 |
| Popis: | Catalysis science is founded on understanding the structure, number, and reactivity of active sites. Kinetic models that consider active sites to be static and noninteracting entities are routinely successful in describing the behavior of heterogeneous catalysts. Yet, active site ensembles often restructure in response to their external environment and even during steady-state catalytic turnover, sometimes requiring non-mean-field kinetic treatments to describe distance-dependent interactions among sites. Such behavior is being recognized more frequently in modern catalysis research, with the advent of experimental methods to quantify turnover rates with increasing precision, an expanding arsenal of operando characterization tools, and computational descriptions of atomic structure and motion at chemical potentials and timescales increasingly relevant to reaction conditions. This review focuses on dynamic changes to metal active site ensembles on zeolite supports, which are silica-based crystalline materials substituted with Al that generate binding sites for isolated and low-nuclearity metal site ensembles. Metal sites can become solvated and mobilized during reaction, facilitating interactions among sites that change their nuclearity and function. Such intersite communication can be regulated by the zeolite support, resulting in non-single-site and potentially non-mean-field kinetic behavior arising from mechanisms of catalytic action that combine elements of those canonically associated with homogeneous and heterogeneous catalysis.We discuss recent literature examples that document dynamic active site behavior in metal-zeolites and outline methodologies to identify and interpret such behavior. We conclude with our outlook on future research directions to develop this evolving branch of catalysis science and harness it for practical applications. |
| Databáze: | OpenAIRE |
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