Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst
Abstract 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 heterogeneo...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38307-w |
| _version_ | 1797832059386855424 |
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| author | Zheng Chen Zhangyun Liu Xin Xu |
| author_facet | Zheng Chen Zhangyun Liu Xin Xu |
| author_sort | Zheng Chen |
| collection | DOAJ |
| description | Abstract 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 Cu1/CeO2 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. |
| first_indexed | 2024-04-09T14:01:41Z |
| format | Article |
| id | doaj.art-f12025d933934cd6aa9d9595c919c4f1 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T14:01:41Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-f12025d933934cd6aa9d9595c919c4f12023-05-07T11:17:58ZengNature PortfolioNature Communications2041-17232023-05-0114111010.1038/s41467-023-38307-wDynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalystZheng Chen0Zhangyun Liu1Xin Xu2Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan UniversityCollaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan UniversityCollaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan UniversityAbstract 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 Cu1/CeO2 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.https://doi.org/10.1038/s41467-023-38307-w |
| spellingShingle | Zheng Chen Zhangyun Liu Xin Xu Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst Nature Communications |
| title | Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst |
| title_full | Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst |
| title_fullStr | Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst |
| title_full_unstemmed | Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst |
| title_short | Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst |
| title_sort | dynamic evolution of the active center driven by hemilabile coordination in cu ceo2 single atom catalyst |
| url | https://doi.org/10.1038/s41467-023-38307-w |
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