A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction
Electrochemical CO2 conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown...
| Main Authors: | , , , , , , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2022
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/163720 |
| _version_ | 1826129507017293824 |
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| author | Gu, Huoliang Shi, Guoshuai Zhong, Lixiang Liu, Lingmei Zhang, Honghao Yang, Chunlei Yu, Ke Zhu, Chenyuan Li, Jiong Zhang, Shuo Chen, Chen Han, Yu Li, Shuzhou Zhang, Liming |
| author2 | School of Materials Science and Engineering |
| author_facet | School of Materials Science and Engineering Gu, Huoliang Shi, Guoshuai Zhong, Lixiang Liu, Lingmei Zhang, Honghao Yang, Chunlei Yu, Ke Zhu, Chenyuan Li, Jiong Zhang, Shuo Chen, Chen Han, Yu Li, Shuzhou Zhang, Liming |
| author_sort | Gu, Huoliang |
| collection | NTU |
| description | Electrochemical CO2 conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown on graphene as a two-dimensional van der Waals heterostructure to catalyze CO2 reduction. Operando X-ray absorption and density functional theory calculations reveal the strong interlayer coupling leads to electron-deficient metal centers and speeds up electrocatalysis. The Co(III)-N4 centers exhibit a CO Faradaic efficiency of 97% at a partial current density of 8.2 mA cm-2 in an H-cell, along with a stable running over 30 h. The selectivity of CO approached 99% with a partial current density of 191 mA cm-2 in a liquid flow cell, and the turnover frequency achieved 50 400 h-1 at -1.15 V vs RHE, outperforming most reported organometallic frameworks. This work highlights the key role of strong electronic coupling between van der Waals layers for accelerating the dynamics of CO2 conversion. |
| first_indexed | 2024-10-01T07:41:25Z |
| format | Journal Article |
| id | ntu-10356/163720 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:41:25Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1637202022-12-15T01:39:15Z A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction Gu, Huoliang Shi, Guoshuai Zhong, Lixiang Liu, Lingmei Zhang, Honghao Yang, Chunlei Yu, Ke Zhu, Chenyuan Li, Jiong Zhang, Shuo Chen, Chen Han, Yu Li, Shuzhou Zhang, Liming School of Materials Science and Engineering Engineering::Materials Metal-Organic Frameworks Carbon-Dioxide Electrochemical CO2 conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown on graphene as a two-dimensional van der Waals heterostructure to catalyze CO2 reduction. Operando X-ray absorption and density functional theory calculations reveal the strong interlayer coupling leads to electron-deficient metal centers and speeds up electrocatalysis. The Co(III)-N4 centers exhibit a CO Faradaic efficiency of 97% at a partial current density of 8.2 mA cm-2 in an H-cell, along with a stable running over 30 h. The selectivity of CO approached 99% with a partial current density of 191 mA cm-2 in a liquid flow cell, and the turnover frequency achieved 50 400 h-1 at -1.15 V vs RHE, outperforming most reported organometallic frameworks. This work highlights the key role of strong electronic coupling between van der Waals layers for accelerating the dynamics of CO2 conversion. This work is funded by the Natural Science Foundation of China (Grants 21872039 and 22072030), Science and Technology Commission of Shanghai Municipality (Grants 18JC1411700, 19DZ2270100, and 22520711100), and the Fundamental Research Funds for the Central Universities (20720220008). 2022-12-15T01:39:15Z 2022-12-15T01:39:15Z 2022 Journal Article Gu, H., Shi, G., Zhong, L., Liu, L., Zhang, H., Yang, C., Yu, K., Zhu, C., Li, J., Zhang, S., Chen, C., Han, Y., Li, S. & Zhang, L. (2022). A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction. Journal of the American Chemical Society, 144(47), 21502-21511. https://dx.doi.org/10.1021/jacs.2c07601 0002-7863 https://hdl.handle.net/10356/163720 10.1021/jacs.2c07601 36332199 2-s2.0-85141720525 47 144 21502 21511 en Journal of the American Chemical Society © 2022 American Chemical Society. All rights reserved. |
| spellingShingle | Engineering::Materials Metal-Organic Frameworks Carbon-Dioxide Gu, Huoliang Shi, Guoshuai Zhong, Lixiang Liu, Lingmei Zhang, Honghao Yang, Chunlei Yu, Ke Zhu, Chenyuan Li, Jiong Zhang, Shuo Chen, Chen Han, Yu Li, Shuzhou Zhang, Liming A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title | A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title_full | A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title_fullStr | A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title_full_unstemmed | A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title_short | A two-dimensional van der Waals heterostructure with isolated electron-deficient cobalt sites toward high-efficiency co2 electroreduction |
| title_sort | two dimensional van der waals heterostructure with isolated electron deficient cobalt sites toward high efficiency co2 electroreduction |
| topic | Engineering::Materials Metal-Organic Frameworks Carbon-Dioxide |
| url | https://hdl.handle.net/10356/163720 |
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