Protecting Copper Oxidation State via Intermediate Confinement for Selective CO2 Electroreduction to C2+ Fuels
Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of couplin...
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| Published in | Journal of the American Chemical Society Vol. 142; no. 13; pp. 6400 - 6408 |
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| Main Authors | , , , , , , , , , , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
American Chemical Society
01.04.2020
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| Abstract | Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of coupling carbon–carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C2+ formation, whereas it is prone to being reduced to Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C2+ Faradaic efficiency of 75.2 ± 2.7% at a C2+ partial current density of 267 ± 13 mA cm–2 and a large C2+-to-C1 ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu+ species in the as-designed catalyst are well retained during CO2 reduction, which leads to the marked C2+ selectivity at a large conversion rate. |
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| AbstractList | Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of coupling carbon–carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C2+ formation, whereas it is prone to being reduced to Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C2+ Faradaic efficiency of 75.2 ± 2.7% at a C2+ partial current density of 267 ± 13 mA cm–2 and a large C2+-to-C1 ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu+ species in the as-designed catalyst are well retained during CO2 reduction, which leads to the marked C2+ selectivity at a large conversion rate. Selective and efficient catalytic conversion of carbon dioxide (CO₂) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO₂ reduction to oxygenates and hydrocarbons (e.g., C₂₊ compounds) is the difficulty of coupling carbon–carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C₂₊ formation, whereas it is prone to being reduced to Cu⁰ at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu⁺ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C₂₊ Faradaic efficiency of 75.2 ± 2.7% at a C₂₊ partial current density of 267 ± 13 mA cm–² and a large C₂₊-to-C₁ ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu⁺ species in the as-designed catalyst are well retained during CO₂ reduction, which leads to the marked C₂₊ selectivity at a large conversion rate. Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of coupling carbon-carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C2+ formation, whereas it is prone to being reduced to Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C2+ Faradaic efficiency of 75.2 ± 2.7% at a C2+ partial current density of 267 ± 13 mA cm-2 and a large C2+-to-C1 ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu+ species in the as-designed catalyst are well retained during CO2 reduction, which leads to the marked C2+ selectivity at a large conversion rate.Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of coupling carbon-carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C2+ formation, whereas it is prone to being reduced to Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C2+ Faradaic efficiency of 75.2 ± 2.7% at a C2+ partial current density of 267 ± 13 mA cm-2 and a large C2+-to-C1 ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu+ species in the as-designed catalyst are well retained during CO2 reduction, which leads to the marked C2+ selectivity at a large conversion rate. |
| Author | Qin, Shuai Zheng, Ya-Rong Wang, Hui-Juan Gao, Fei-Yue Liu, Ren Yang, Peng-Peng Yu, Xingxing Zhu, Jun-Fa Zhang, Xiao-Long Niu, Zhuang-Zhuang Wu, Zhi-Zheng Ma, Tao Chi, Li-Ping Duan, Yu Zheng, Xu-Sheng Gao, Min-Rui Yu, Shu-Hong |
| AuthorAffiliation | Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry Experimental Center of Engineering and Material Science National Synchrotron Radiation Laboratory Dalian National Laboratory for Clean Energy |
| AuthorAffiliation_xml | – name: Dalian National Laboratory for Clean Energy – name: National Synchrotron Radiation Laboratory – name: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – name: Experimental Center of Engineering and Material Science |
| Author_xml | – sequence: 1 givenname: Peng-Peng surname: Yang fullname: Yang, Peng-Peng organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 2 givenname: Xiao-Long surname: Zhang fullname: Zhang, Xiao-Long organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 3 givenname: Fei-Yue surname: Gao fullname: Gao, Fei-Yue organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 4 givenname: Ya-Rong surname: Zheng fullname: Zheng, Ya-Rong organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 5 givenname: Zhuang-Zhuang surname: Niu fullname: Niu, Zhuang-Zhuang organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 6 givenname: Xingxing surname: Yu fullname: Yu, Xingxing organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 7 givenname: Ren surname: Liu fullname: Liu, Ren organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 8 givenname: Zhi-Zheng surname: Wu fullname: Wu, Zhi-Zheng organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 9 givenname: Shuai surname: Qin fullname: Qin, Shuai organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 10 givenname: Li-Ping surname: Chi fullname: Chi, Li-Ping organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 11 givenname: Yu surname: Duan fullname: Duan, Yu organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 12 givenname: Tao surname: Ma fullname: Ma, Tao organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 13 givenname: Xu-Sheng surname: Zheng fullname: Zheng, Xu-Sheng organization: National Synchrotron Radiation Laboratory – sequence: 14 givenname: Jun-Fa orcidid: 0000-0003-0888-4261 surname: Zhu fullname: Zhu, Jun-Fa organization: National Synchrotron Radiation Laboratory – sequence: 15 givenname: Hui-Juan surname: Wang fullname: Wang, Hui-Juan organization: Experimental Center of Engineering and Material Science – sequence: 16 givenname: Min-Rui orcidid: 0000-0002-7805-803X surname: Gao fullname: Gao, Min-Rui email: mgao@ustc.edu.cn organization: Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry – sequence: 17 givenname: Shu-Hong orcidid: 0000-0003-3732-1011 surname: Yu fullname: Yu, Shu-Hong email: shyu@ustc.edu.cn organization: Dalian National Laboratory for Clean Energy |
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| Snippet | Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable... Selective and efficient catalytic conversion of carbon dioxide (CO₂) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable... |
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| SubjectTerms | carbon carbon dioxide catalysts catalytic activity chemical bonding copper cuprous oxide feedstocks fuels hydrocarbons oxidation Raman spectroscopy renewable energy sources value added X-ray absorption spectroscopy |
| Title | Protecting Copper Oxidation State via Intermediate Confinement for Selective CO2 Electroreduction to C2+ Fuels |
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