Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
Abstract
The electroreduction of CO_2 is a promising technology for carbon utilization. Although electrolysis of CO_2 or CO_2-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 NH_3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH_3 to a surface-bound ketene intermediate, a step that is in competition with OH– addition, which leads to acetate. 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 CO_2 reduction.
Additional Information
© 2019 Springer Nature Publishing AG. Received 21 January 2019; Accepted 10 July 2019; Published 23 August 2019. F.J. would like to thank W. Luc for illustration assistance and E. Jeng for help with preparation of the anode. M.J. and J.-J.L. also thank B. Murphy and Z. J. Wang for help with GC–MS. The experimental work was financially supported by the US Department of Energy under award no. DE-FE0029868. F.J. also thanks the National Science Foundation Faculty Early Career Development program (award no. CBET-1350911). J.-J.L. acknowledges financial support from Chinese Scholarship Council. T.C. and W.A.G. were supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. This work used the Extreme Science and Engineering Discovery Environment, which is supported by National Science Foundation grant no. ACI-1053575. This research used resources at the 8-ID Beamline of the National Synchrotron Light Source II, a US Department of Energy Office of Science User Facility operated by Brookhaven National Laboratory under contract no. DE-SC0012704. The authors acknowledge E. Stavitski (8-ID Beamline, NSLS-II, Brookhaven National Laboratory) for assistance in X-ray absorption spectroscopy measurements. Data availability: The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request. Code availability: The computational codes used in the current study are available from the corresponding author on reasonable request. Competing interests: M.J., J.-J.L. and F.J. have filed a patent application (international patent application number: PCT/US 19/27012) that is based on the discovery presented in this work.Attached Files
Supplemental Material - 41557_2019_312_MOESM1_ESM.pdf
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Additional details
- Eprint ID
- 96601
- Resolver ID
- CaltechAUTHORS:20190620-142925725
- Department of Energy (DOE)
- DE-FE0029868
- NSF
- CBET-1350911
- Chinese Scholarship Council
- Joint Center for Artificial Photosynthesis (JCAP)
- Department of Energy (DOE)
- DE-SC0004993
- NSF
- ACI-1053575
- Department of Energy (DOE)
- DE-SC0012704
- Created
-
2019-08-23Created from EPrint's datestamp field
- Updated
-
2021-11-16Created from EPrint's last_modified field
- Caltech groups
- JCAP
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 1349