Optimizing the reaction pathway of methane photo-oxidation over single copper sites
Abstract Direct photocatalytic conversion of methane to value-added C1 oxygenate with O2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coor...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-10-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-53483-z |
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| author | Chengyang Feng Shouwei Zuo Miao Hu Yuanfu Ren Liwei Xia Jun Luo Chen Zou Sibo Wang Yihan Zhu Magnus Rueping Yu Han Huabin Zhang |
| author_facet | Chengyang Feng Shouwei Zuo Miao Hu Yuanfu Ren Liwei Xia Jun Luo Chen Zou Sibo Wang Yihan Zhu Magnus Rueping Yu Han Huabin Zhang |
| author_sort | Chengyang Feng |
| collection | DOAJ |
| description | Abstract Direct photocatalytic conversion of methane to value-added C1 oxygenate with O2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH4 to HCHO. We propose the directional activation of O2 on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward •OOH. The synchronously generated •OOH and •CH3 radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol gcat −1 h−1. This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH4 photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand. |
| format | Article |
| id | doaj-art-5fcf7ab33be64d438dbc7b8bcaaf1d31 |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-5fcf7ab33be64d438dbc7b8bcaaf1d312025-08-20T02:11:25ZengNature PortfolioNature Communications2041-17232024-10-0115111110.1038/s41467-024-53483-zOptimizing the reaction pathway of methane photo-oxidation over single copper sitesChengyang Feng0Shouwei Zuo1Miao Hu2Yuanfu Ren3Liwei Xia4Jun Luo5Chen Zou6Sibo Wang7Yihan Zhu8Magnus Rueping9Yu Han10Huabin Zhang11Center for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyCenter for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyCenter for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyCenter for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyCenter for Electron Microscopy, Institute for Frontier and Interdisciplinary Sciences, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of TechnologyState Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, MOE Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, and School of Resources, Environment and Materials, Guangxi UniversityCenter for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyState Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou UniversityCenter for Electron Microscopy, Institute for Frontier and Interdisciplinary Sciences, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of TechnologyKAUST Catalysis Center (KCC), Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST)Electron Microscopy Center, South China University of TechnologyCenter for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division, King Abdullah University of Science and TechnologyAbstract Direct photocatalytic conversion of methane to value-added C1 oxygenate with O2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH4 to HCHO. We propose the directional activation of O2 on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward •OOH. The synchronously generated •OOH and •CH3 radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol gcat −1 h−1. This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH4 photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand.https://doi.org/10.1038/s41467-024-53483-z |
| spellingShingle | Chengyang Feng Shouwei Zuo Miao Hu Yuanfu Ren Liwei Xia Jun Luo Chen Zou Sibo Wang Yihan Zhu Magnus Rueping Yu Han Huabin Zhang Optimizing the reaction pathway of methane photo-oxidation over single copper sites Nature Communications |
| title | Optimizing the reaction pathway of methane photo-oxidation over single copper sites |
| title_full | Optimizing the reaction pathway of methane photo-oxidation over single copper sites |
| title_fullStr | Optimizing the reaction pathway of methane photo-oxidation over single copper sites |
| title_full_unstemmed | Optimizing the reaction pathway of methane photo-oxidation over single copper sites |
| title_short | Optimizing the reaction pathway of methane photo-oxidation over single copper sites |
| title_sort | optimizing the reaction pathway of methane photo oxidation over single copper sites |
| url | https://doi.org/10.1038/s41467-024-53483-z |
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