Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion
Abstract Electrochemical carbon monoxide (CO) reduction to high-energy-density fuels provides a potential way for chemical production and intermittent energy storage. As a valuable C3 species, n-propanol still suffers from a relatively low Faradaic efficiency (FE), sluggish conversion rate and poor...
| Main Authors: | , , , , , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-08-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-40689-w |
| _version_ | 1797558194713657344 |
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| author | Wenzhe Niu Zheng Chen Wen Guo Wei Mao Yi Liu Yunna Guo Jingzhao Chen Rui Huang Lin Kang Yiwen Ma Qisheng Yan Jinyu Ye Chunyu Cui Liqiang Zhang Peng Wang Xin Xu Bo Zhang |
| author_facet | Wenzhe Niu Zheng Chen Wen Guo Wei Mao Yi Liu Yunna Guo Jingzhao Chen Rui Huang Lin Kang Yiwen Ma Qisheng Yan Jinyu Ye Chunyu Cui Liqiang Zhang Peng Wang Xin Xu Bo Zhang |
| author_sort | Wenzhe Niu |
| collection | DOAJ |
| description | Abstract Electrochemical carbon monoxide (CO) reduction to high-energy-density fuels provides a potential way for chemical production and intermittent energy storage. As a valuable C3 species, n-propanol still suffers from a relatively low Faradaic efficiency (FE), sluggish conversion rate and poor stability. Herein, we introduce an “atomic size misfit” strategy to modulate active sites, and report a facile synthesis of a Pb-doped Cu catalyst with numerous atomic Pb-concentrated grain boundaries. Operando spectroscopy studies demonstrate that these Pb-rich Cu-grain boundary sites exhibit stable low coordination and can achieve a stronger CO adsorption for a higher surface CO coverage. Using this Pb-Cu catalyst, we achieve a CO-to-n-propanol FE (FEpropanol) of 47 ± 3% and a half-cell energy conversion efficiency (EE) of 25% in a flow cell. When applied in a membrane electrode assembly (MEA) device, a stable FEpropanol above 30% and the corresponding full-cell EE of over 16% are maintained for over 100 h with the n-propanol partial current above 300 mA (5 cm2 electrode). Furthermore, operando X-ray absorption spectroscopy and theoretical studies reveal that the structurally-flexible Pb-Cu surface can adaptively stabilize the key intermediates, which strengthens the *CO binding while maintaining the C–C coupling ability, thus promoting the CO-to-n-propanol conversion. |
| first_indexed | 2024-03-10T17:27:53Z |
| format | Article |
| id | doaj.art-ecbb4cefbce843ffa84ad4719b5c3f38 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:27:53Z |
| publishDate | 2023-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-ecbb4cefbce843ffa84ad4719b5c3f382023-11-20T10:08:15ZengNature PortfolioNature Communications2041-17232023-08-0114111210.1038/s41467-023-40689-wPb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversionWenzhe Niu0Zheng Chen1Wen Guo2Wei Mao3Yi Liu4Yunna Guo5Jingzhao Chen6Rui Huang7Lin Kang8Yiwen Ma9Qisheng Yan10Jinyu Ye11Chunyu Cui12Liqiang Zhang13Peng Wang14Xin Xu15Bo Zhang16State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityDepartment of Chemistry, MOE Key Laboratory of Computational Physical Sciences, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityNational Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures, Nanjing UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityClean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan UniversityClean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityCollege of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityClean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan UniversityNational Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures, Nanjing UniversityDepartment of Chemistry, MOE Key Laboratory of Computational Physical Sciences, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan UniversityState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan UniversityAbstract Electrochemical carbon monoxide (CO) reduction to high-energy-density fuels provides a potential way for chemical production and intermittent energy storage. As a valuable C3 species, n-propanol still suffers from a relatively low Faradaic efficiency (FE), sluggish conversion rate and poor stability. Herein, we introduce an “atomic size misfit” strategy to modulate active sites, and report a facile synthesis of a Pb-doped Cu catalyst with numerous atomic Pb-concentrated grain boundaries. Operando spectroscopy studies demonstrate that these Pb-rich Cu-grain boundary sites exhibit stable low coordination and can achieve a stronger CO adsorption for a higher surface CO coverage. Using this Pb-Cu catalyst, we achieve a CO-to-n-propanol FE (FEpropanol) of 47 ± 3% and a half-cell energy conversion efficiency (EE) of 25% in a flow cell. When applied in a membrane electrode assembly (MEA) device, a stable FEpropanol above 30% and the corresponding full-cell EE of over 16% are maintained for over 100 h with the n-propanol partial current above 300 mA (5 cm2 electrode). Furthermore, operando X-ray absorption spectroscopy and theoretical studies reveal that the structurally-flexible Pb-Cu surface can adaptively stabilize the key intermediates, which strengthens the *CO binding while maintaining the C–C coupling ability, thus promoting the CO-to-n-propanol conversion.https://doi.org/10.1038/s41467-023-40689-w |
| spellingShingle | Wenzhe Niu Zheng Chen Wen Guo Wei Mao Yi Liu Yunna Guo Jingzhao Chen Rui Huang Lin Kang Yiwen Ma Qisheng Yan Jinyu Ye Chunyu Cui Liqiang Zhang Peng Wang Xin Xu Bo Zhang Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion Nature Communications |
| title | Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion |
| title_full | Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion |
| title_fullStr | Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion |
| title_full_unstemmed | Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion |
| title_short | Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion |
| title_sort | pb rich cu grain boundary sites for selective co to n propanol electroconversion |
| url | https://doi.org/10.1038/s41467-023-40689-w |
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