Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites
Abstract Electrocatalytic reduction of waste nitrates (NO3 −) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, th...
| Main Authors: | , , , , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-40174-4 |
| _version_ | 1797769428406894592 |
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| author | Eamonn Murphy Yuanchao Liu Ivana Matanovic Martina Rüscher Ying Huang Alvin Ly Shengyuan Guo Wenjie Zang Xingxu Yan Andrea Martini Janis Timoshenko Beatriz Roldán Cuenya Iryna V. Zenyuk Xiaoqing Pan Erik D. Spoerke Plamen Atanassov |
| author_facet | Eamonn Murphy Yuanchao Liu Ivana Matanovic Martina Rüscher Ying Huang Alvin Ly Shengyuan Guo Wenjie Zang Xingxu Yan Andrea Martini Janis Timoshenko Beatriz Roldán Cuenya Iryna V. Zenyuk Xiaoqing Pan Erik D. Spoerke Plamen Atanassov |
| author_sort | Eamonn Murphy |
| collection | DOAJ |
| description | Abstract Electrocatalytic reduction of waste nitrates (NO3 −) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO3 − reduction to NH3 in neutral media, with a specific focus on deciphering the role of the NO2 − intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO2 − reduction activity and NO3 − reduction selectivity for NH3. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO2 − evolution, over the normal M-N4 sites and their oxo-form (O-M-N4) for oxyphilic metals. This work provides a platform for designing multi-element NO3RR cascades with single-atom sites or their hybridization with extended catalytic surfaces. |
| first_indexed | 2024-03-12T21:08:52Z |
| format | Article |
| id | doaj.art-4d9f7ab670384400b946c7d7021862e0 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-12T21:08:52Z |
| publishDate | 2023-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-4d9f7ab670384400b946c7d7021862e02023-07-30T11:19:11ZengNature PortfolioNature Communications2041-17232023-07-0114111510.1038/s41467-023-40174-4Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sitesEamonn Murphy0Yuanchao Liu1Ivana Matanovic2Martina Rüscher3Ying Huang4Alvin Ly5Shengyuan Guo6Wenjie Zang7Xingxu Yan8Andrea Martini9Janis Timoshenko10Beatriz Roldán Cuenya11Iryna V. Zenyuk12Xiaoqing Pan13Erik D. Spoerke14Plamen Atanassov15Department of Chemical and Biomolecular Engineering, University of CaliforniaDepartment of Chemical and Biomolecular Engineering, University of CaliforniaDepartment of Chemical and Biological Engineering, University of New MexicoDepartment of Interface Science, Fritz Haber Institute of the Max Planck SocietyDepartment of Materials Science and Engineering, University of CaliforniaDepartment of Materials Science and Engineering, University of CaliforniaDepartment of Chemical and Biomolecular Engineering, University of CaliforniaDepartment of Materials Science and Engineering, University of CaliforniaDepartment of Materials Science and Engineering, University of CaliforniaDepartment of Interface Science, Fritz Haber Institute of the Max Planck SocietyDepartment of Interface Science, Fritz Haber Institute of the Max Planck SocietyDepartment of Interface Science, Fritz Haber Institute of the Max Planck SocietyDepartment of Chemical and Biomolecular Engineering, University of CaliforniaDepartment of Materials Science and Engineering, University of CaliforniaSandia National LaboratoriesDepartment of Chemical and Biomolecular Engineering, University of CaliforniaAbstract Electrocatalytic reduction of waste nitrates (NO3 −) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO3 − reduction to NH3 in neutral media, with a specific focus on deciphering the role of the NO2 − intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO2 − reduction activity and NO3 − reduction selectivity for NH3. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO2 − evolution, over the normal M-N4 sites and their oxo-form (O-M-N4) for oxyphilic metals. This work provides a platform for designing multi-element NO3RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.https://doi.org/10.1038/s41467-023-40174-4 |
| spellingShingle | Eamonn Murphy Yuanchao Liu Ivana Matanovic Martina Rüscher Ying Huang Alvin Ly Shengyuan Guo Wenjie Zang Xingxu Yan Andrea Martini Janis Timoshenko Beatriz Roldán Cuenya Iryna V. Zenyuk Xiaoqing Pan Erik D. Spoerke Plamen Atanassov Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites Nature Communications |
| title | Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites |
| title_full | Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites |
| title_fullStr | Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites |
| title_full_unstemmed | Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites |
| title_short | Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites |
| title_sort | elucidating electrochemical nitrate and nitrite reduction over atomically dispersed transition metal sites |
| url | https://doi.org/10.1038/s41467-023-40174-4 |
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