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Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst

Hemilability is an important concept in homogeneous catalysis where both the reactant activation and the product formation can occur simultaneously through a reversible opening and closing of the metal-ligand coordination sphere. However, this effect has rarely been discussed in heterogeneous cataly...

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Autores principales: Chen, Zheng, Liu, Zhangyun, Xu, Xin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10154346/
https://www.ncbi.nlm.nih.gov/pubmed/37130833
http://dx.doi.org/10.1038/s41467-023-38307-w
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author Chen, Zheng
Liu, Zhangyun
Xu, Xin
author_facet Chen, Zheng
Liu, Zhangyun
Xu, Xin
author_sort Chen, Zheng
collection PubMed
description Hemilability is an important concept in homogeneous catalysis where both the reactant activation and the product formation can occur simultaneously through a reversible opening and closing of the metal-ligand coordination sphere. However, this effect has rarely been discussed in heterogeneous catalysis. Here, by employing a theoretical study on CO oxidation over substituted Cu(1)/CeO(2) single atom catalysts, we show that dynamic evolution of metal-support coordination can significantly change the electronic structure of the active center. The evolution of the active center is shown to either strengthen or weaken the metal-adsorbate bonding as the reaction proceeds from reactants, through intermediates, to products. As a result, the activity of the catalyst can be increased. We explain our observations by extending hemilability effects to single atom heterogenous catalysts and anticipate that introducing this concept can offer a new insight into the important role active site dynamics have in catalysis toward the rational design of more sophisticated single atom catalyst materials.
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spelling pubmed-101543462023-05-04 Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst Chen, Zheng Liu, Zhangyun Xu, Xin Nat Commun Article Hemilability is an important concept in homogeneous catalysis where both the reactant activation and the product formation can occur simultaneously through a reversible opening and closing of the metal-ligand coordination sphere. However, this effect has rarely been discussed in heterogeneous catalysis. Here, by employing a theoretical study on CO oxidation over substituted Cu(1)/CeO(2) single atom catalysts, we show that dynamic evolution of metal-support coordination can significantly change the electronic structure of the active center. The evolution of the active center is shown to either strengthen or weaken the metal-adsorbate bonding as the reaction proceeds from reactants, through intermediates, to products. As a result, the activity of the catalyst can be increased. We explain our observations by extending hemilability effects to single atom heterogenous catalysts and anticipate that introducing this concept can offer a new insight into the important role active site dynamics have in catalysis toward the rational design of more sophisticated single atom catalyst materials. Nature Publishing Group UK 2023-05-02 /pmc/articles/PMC10154346/ /pubmed/37130833 http://dx.doi.org/10.1038/s41467-023-38307-w Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Chen, Zheng
Liu, Zhangyun
Xu, Xin
Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title_full Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title_fullStr Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title_full_unstemmed Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title_short Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO(2) single-atom catalyst
title_sort dynamic evolution of the active center driven by hemilabile coordination in cu/ceo(2) single-atom catalyst
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10154346/
https://www.ncbi.nlm.nih.gov/pubmed/37130833
http://dx.doi.org/10.1038/s41467-023-38307-w
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