Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
Abstract
The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C–C bond formation. Here, we demonstrate that C–N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH– addition, which leads to acetate. Here, the C–N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon–heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.
- Authors:
-
[1];
[2];
[3];
[1];
[4];
[5];
[1]
- Univ. of Delaware, Newark, DE (United States)
- Univ. of Delaware, Newark, DE (United States); Nanjing Univ. (China)
- California Institute of Technology (CalTech), Pasadena, CA (United States); Soochow Univ., Jiangsu (China)
- Nanjing Univ. (China)
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Delaware, Newark, DE (United States); Nanjing Univ. (China); California Institute of Technology (CalTech), Pasadena, CA (United States); Soochow Univ., Jiangsu (China)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1712668
- Grant/Contract Number:
- SC0004993; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Chemistry
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 9; Journal ID: ISSN 1755-4330
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon dioxide; carbon monoxide; electrocatalysts; electrochemical reduction; chemical engineering
Citation Formats
Jouny, Matthew, Lv, Jing-Jing, Cheng, Tao, Ko, Byung Hee, Zhu, Jun-Jie, Goddard, III, William A., and Jiao, Feng. Formation of carbon–nitrogen bonds in carbon monoxide electrolysis. United States: N. p., 2019.
Web. doi:10.1038/s41557-019-0312-z.
Jouny, Matthew, Lv, Jing-Jing, Cheng, Tao, Ko, Byung Hee, Zhu, Jun-Jie, Goddard, III, William A., & Jiao, Feng. Formation of carbon–nitrogen bonds in carbon monoxide electrolysis. United States. https://doi.org/10.1038/s41557-019-0312-z
Jouny, Matthew, Lv, Jing-Jing, Cheng, Tao, Ko, Byung Hee, Zhu, Jun-Jie, Goddard, III, William A., and Jiao, Feng. Fri .
"Formation of carbon–nitrogen bonds in carbon monoxide electrolysis". United States. https://doi.org/10.1038/s41557-019-0312-z. https://www.osti.gov/servlets/purl/1712668.
@article{osti_1712668,
title = {Formation of carbon–nitrogen bonds in carbon monoxide electrolysis},
author = {Jouny, Matthew and Lv, Jing-Jing and Cheng, Tao and Ko, Byung Hee and Zhu, Jun-Jie and Goddard, III, William A. and Jiao, Feng},
abstractNote = {The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C–C bond formation. Here, we demonstrate that C–N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH– addition, which leads to acetate. Here, the C–N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon–heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.},
doi = {10.1038/s41557-019-0312-z},
journal = {Nature Chemistry},
number = 9,
volume = 11,
place = {United States},
year = {Fri Aug 23 00:00:00 EDT 2019},
month = {Fri Aug 23 00:00:00 EDT 2019}
}
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Works referencing / citing this record:
Carbon monoxide electroreduction as an emerging platform for carbon utilization
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