Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling
Abstract Cu catalyses electrochemical CO2 reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six pheny...
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| Format: | Article |
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Nature Portfolio
2024-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-50791-2 |
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| author | Yu Yang Cheng Zhang Chengyi Zhang Yaohui Shi Jun Li Bernt Johannessen Yongxiang Liang Shuzhen Zhang Qiang Song Haowei Zhang Jialei Huang Jingwen Ke Lei Zhang Qingqing Song Jianrong Zeng Ying Zhang Zhigang Geng Pu-Sheng Wang Ziyun Wang Jie Zeng Fengwang Li |
| author_facet | Yu Yang Cheng Zhang Chengyi Zhang Yaohui Shi Jun Li Bernt Johannessen Yongxiang Liang Shuzhen Zhang Qiang Song Haowei Zhang Jialei Huang Jingwen Ke Lei Zhang Qingqing Song Jianrong Zeng Ying Zhang Zhigang Geng Pu-Sheng Wang Ziyun Wang Jie Zeng Fengwang Li |
| author_sort | Yu Yang |
| collection | DOAJ |
| description | Abstract Cu catalyses electrochemical CO2 reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six phenyl-1H-1,2,3-triazole derivatives to form stable coordination polymer catalysts with homogenized, single-site Cu active sites. Electronic structure modelling, X-ray absorption spectroscopy, and ultraviolet–visible spectroscopy show a widely tuneable Cu electronics by modulating the highest occupied molecular orbital energy of ligands. Using CO diffuse reflectance Fourier transform infrared spectroscopy, in-situ Raman spectroscopy, and density functional theory calculations, we find that the binding strength of *CO intermediate is positively correlated to highest occupied molecular orbital energies of the ligands. As a result, we enable a tuning of C–C coupling efficiency—a parameter we define to evaluate the efficiency of C2 production—in a broad range of 0.26 to 0.86. This work establishes a molecular platform that allows for studying structure-function relationships in CO2 electrolysis and devises new catalyst design strategies appliable to other electrocatalysis. |
| format | Article |
| id | doaj-art-a12eac01c620445cb8963c36d093c9ec |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a12eac01c620445cb8963c36d093c9ec2025-01-12T12:29:31ZengNature PortfolioNature Communications2041-17232024-07-0115111110.1038/s41467-024-50791-2Ligand-tuning copper in coordination polymers for efficient electrochemical C–C couplingYu Yang0Cheng Zhang1Chengyi Zhang2Yaohui Shi3Jun Li4Bernt Johannessen5Yongxiang Liang6Shuzhen Zhang7Qiang Song8Haowei Zhang9Jialei Huang10Jingwen Ke11Lei Zhang12Qingqing Song13Jianrong Zeng14Ying Zhang15Zhigang Geng16Pu-Sheng Wang17Ziyun Wang18Jie Zeng19Fengwang Li20School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneyHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaSchool of Chemical Sciences, University of AucklandHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaFrontiers Science Center for Transformative Molecules, Shanghai Jiao Tong UniversityAustralian Synchrotron, ANSTOHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaSchool of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneySchool of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneySchool of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneySchool of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneyHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaKey Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan UniversityShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesKey Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan UniversityHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaSchool of Chemical Sciences, University of AucklandHefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry and Chemical Physics, University of Science and Technology of ChinaSchool of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of SydneyAbstract Cu catalyses electrochemical CO2 reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six phenyl-1H-1,2,3-triazole derivatives to form stable coordination polymer catalysts with homogenized, single-site Cu active sites. Electronic structure modelling, X-ray absorption spectroscopy, and ultraviolet–visible spectroscopy show a widely tuneable Cu electronics by modulating the highest occupied molecular orbital energy of ligands. Using CO diffuse reflectance Fourier transform infrared spectroscopy, in-situ Raman spectroscopy, and density functional theory calculations, we find that the binding strength of *CO intermediate is positively correlated to highest occupied molecular orbital energies of the ligands. As a result, we enable a tuning of C–C coupling efficiency—a parameter we define to evaluate the efficiency of C2 production—in a broad range of 0.26 to 0.86. This work establishes a molecular platform that allows for studying structure-function relationships in CO2 electrolysis and devises new catalyst design strategies appliable to other electrocatalysis.https://doi.org/10.1038/s41467-024-50791-2 |
| spellingShingle | Yu Yang Cheng Zhang Chengyi Zhang Yaohui Shi Jun Li Bernt Johannessen Yongxiang Liang Shuzhen Zhang Qiang Song Haowei Zhang Jialei Huang Jingwen Ke Lei Zhang Qingqing Song Jianrong Zeng Ying Zhang Zhigang Geng Pu-Sheng Wang Ziyun Wang Jie Zeng Fengwang Li Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling Nature Communications |
| title | Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling |
| title_full | Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling |
| title_fullStr | Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling |
| title_full_unstemmed | Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling |
| title_short | Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling |
| title_sort | ligand tuning copper in coordination polymers for efficient electrochemical c c coupling |
| url | https://doi.org/10.1038/s41467-024-50791-2 |
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