Operando TEM study of a working copper catalyst during ethylene oxidation
Abstract Active catalysts are typically metastable, and their surface state depends on the gas-phase chemical potential and reaction kinetics. To gain relevant insights into structure-performance relationships, it is essential to investigate catalysts under their operational conditions. Here, we use...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57418-0 |
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| author | Wenqian Yu Shengnan Yue Minghe Yang Masahiro Hashimoto Panpan Liu Li Zhu Wangjing Xie Travis Jones Marc Willinger Xing Huang |
| author_facet | Wenqian Yu Shengnan Yue Minghe Yang Masahiro Hashimoto Panpan Liu Li Zhu Wangjing Xie Travis Jones Marc Willinger Xing Huang |
| author_sort | Wenqian Yu |
| collection | DOAJ |
| description | Abstract Active catalysts are typically metastable, and their surface state depends on the gas-phase chemical potential and reaction kinetics. To gain relevant insights into structure-performance relationships, it is essential to investigate catalysts under their operational conditions. Here, we use operando TEM combining real-time observations with online mass spectrometry (MS) to study a Cu catalyst during ethylene oxidation. We identify three distinct regimes characterized by varying structures and states that show different selectivities with temperature, and elucidate the reaction pathways with the aid of theoretical calculations. Our findings reveal that quasi-static Cu2O at low temperatures is selective towards ethylene oxide (EO) and acetaldehyde (AcH) via an oxometallacycle (OMC) pathway. In the dynamic Cu0/Cu2O oscillation regime at medium temperatures, partially reduced and strained oxides decrease the activation energies associated with partial oxidation. At high temperatures, the catalyst is predominantly Cu0, partially covered by a monolayer Cu2O. While Cu0 is extremely efficient in dehydrogenation and eventual combustion, the monolayer oxide favors direct EO formation. These results challenge conclusions drawn from ultra-high vacuum studies that suggested metallic copper would be a selective epoxidation catalyst and highlight the need for operando study under realistic conditions. |
| format | Article |
| id | doaj-art-da3daee36ded4710a5fc3ce7371ef7fc |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-da3daee36ded4710a5fc3ce7371ef7fc2025-08-20T03:10:06ZengNature PortfolioNature Communications2041-17232025-02-0116111110.1038/s41467-025-57418-0Operando TEM study of a working copper catalyst during ethylene oxidationWenqian Yu0Shengnan Yue1Minghe Yang2Masahiro Hashimoto3Panpan Liu4Li Zhu5Wangjing Xie6Travis Jones7Marc Willinger8Xing Huang9College of Chemistry, Fuzhou UniversityCollege of Chemistry, Fuzhou UniversityCollege of Chemistry, Fuzhou UniversityJEOL (EUROPE) SAS, allée de GivernyCollege of Chemistry, Fuzhou UniversityCollege of Chemistry, Fuzhou UniversityCollege of Chemistry, Fuzhou UniversityTheoretical Division, Los Alamos National LaboratoryDepartment of Chemistry, Technical University of MunichCollege of Chemistry, Fuzhou UniversityAbstract Active catalysts are typically metastable, and their surface state depends on the gas-phase chemical potential and reaction kinetics. To gain relevant insights into structure-performance relationships, it is essential to investigate catalysts under their operational conditions. Here, we use operando TEM combining real-time observations with online mass spectrometry (MS) to study a Cu catalyst during ethylene oxidation. We identify three distinct regimes characterized by varying structures and states that show different selectivities with temperature, and elucidate the reaction pathways with the aid of theoretical calculations. Our findings reveal that quasi-static Cu2O at low temperatures is selective towards ethylene oxide (EO) and acetaldehyde (AcH) via an oxometallacycle (OMC) pathway. In the dynamic Cu0/Cu2O oscillation regime at medium temperatures, partially reduced and strained oxides decrease the activation energies associated with partial oxidation. At high temperatures, the catalyst is predominantly Cu0, partially covered by a monolayer Cu2O. While Cu0 is extremely efficient in dehydrogenation and eventual combustion, the monolayer oxide favors direct EO formation. These results challenge conclusions drawn from ultra-high vacuum studies that suggested metallic copper would be a selective epoxidation catalyst and highlight the need for operando study under realistic conditions.https://doi.org/10.1038/s41467-025-57418-0 |
| spellingShingle | Wenqian Yu Shengnan Yue Minghe Yang Masahiro Hashimoto Panpan Liu Li Zhu Wangjing Xie Travis Jones Marc Willinger Xing Huang Operando TEM study of a working copper catalyst during ethylene oxidation Nature Communications |
| title | Operando TEM study of a working copper catalyst during ethylene oxidation |
| title_full | Operando TEM study of a working copper catalyst during ethylene oxidation |
| title_fullStr | Operando TEM study of a working copper catalyst during ethylene oxidation |
| title_full_unstemmed | Operando TEM study of a working copper catalyst during ethylene oxidation |
| title_short | Operando TEM study of a working copper catalyst during ethylene oxidation |
| title_sort | operando tem study of a working copper catalyst during ethylene oxidation |
| url | https://doi.org/10.1038/s41467-025-57418-0 |
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