Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction
© 2019 The Royal Society of Chemistry. Electrochemical carbon dioxide reduction enables conversion of carbon dioxide into fuels and chemicals with renewable energy input. Cobalt-based molecular complexes have exhibited high selectivity, activity, and stability for transforming carbon dioxide into ca...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Royal Society of Chemistry (RSC)
2021
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| Online Access: | https://hdl.handle.net/1721.1/135133 |
| _version_ | 1826215244882509824 |
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| author | Zhu, Minghui Yang, Deng-Tao Ye, Ruquan Zeng, Joy Corbin, Nathan Manthiram, Karthish |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Zhu, Minghui Yang, Deng-Tao Ye, Ruquan Zeng, Joy Corbin, Nathan Manthiram, Karthish |
| author_sort | Zhu, Minghui |
| collection | MIT |
| description | © 2019 The Royal Society of Chemistry. Electrochemical carbon dioxide reduction enables conversion of carbon dioxide into fuels and chemicals with renewable energy input. Cobalt-based molecular complexes have exhibited high selectivity, activity, and stability for transforming carbon dioxide into carbon monoxide. Through evaluating immobilized cobalt porphyrins functionalized with various peripheral substituents, we demonstrated that their activity is affected not only by the electronegativity of the substituents, but importantly, also by the charge of the substituents. The performance of immobilized cobalt porphyrins can be improved by introducing electron-donating and positively charged functional groups. Through kinetic studies, we were able to understand the mechanism by which electron-donating groups enhance the observed rates of carbon dioxide reduction and how cationic functionality may contribute towards electrostatic stabilization of the intermediate formed in the rate-determining step. Our methodology provides a robust and experimentally-verified method of computationally predicting the electronic effect of peripheral substitution and hence the catalytic activity of substituted porphyrins. |
| first_indexed | 2024-09-23T16:20:03Z |
| format | Article |
| id | mit-1721.1/135133 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:20:03Z |
| publishDate | 2021 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1351332023-02-22T17:32:49Z Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction Zhu, Minghui Yang, Deng-Tao Ye, Ruquan Zeng, Joy Corbin, Nathan Manthiram, Karthish Massachusetts Institute of Technology. Department of Chemical Engineering © 2019 The Royal Society of Chemistry. Electrochemical carbon dioxide reduction enables conversion of carbon dioxide into fuels and chemicals with renewable energy input. Cobalt-based molecular complexes have exhibited high selectivity, activity, and stability for transforming carbon dioxide into carbon monoxide. Through evaluating immobilized cobalt porphyrins functionalized with various peripheral substituents, we demonstrated that their activity is affected not only by the electronegativity of the substituents, but importantly, also by the charge of the substituents. The performance of immobilized cobalt porphyrins can be improved by introducing electron-donating and positively charged functional groups. Through kinetic studies, we were able to understand the mechanism by which electron-donating groups enhance the observed rates of carbon dioxide reduction and how cationic functionality may contribute towards electrostatic stabilization of the intermediate formed in the rate-determining step. Our methodology provides a robust and experimentally-verified method of computationally predicting the electronic effect of peripheral substitution and hence the catalytic activity of substituted porphyrins. 2021-10-27T20:10:52Z 2021-10-27T20:10:52Z 2019 2019-04-24T14:06:56Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/135133 en 10.1039/c9cy00102f Catalysis Science & Technology Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Zhu, Minghui Yang, Deng-Tao Ye, Ruquan Zeng, Joy Corbin, Nathan Manthiram, Karthish Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title | Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title_full | Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title_fullStr | Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title_full_unstemmed | Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title_short | Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| title_sort | inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction |
| url | https://hdl.handle.net/1721.1/135133 |
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