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Formation of carbon–nitrogen bonds in carbon monoxide electrolysis

Jouny, Matthew and Lv, Jing-Jing and Cheng, Tao and Ko, Byung Hee and Zhu, Jun-Jie and Goddard, William A., III and Jiao, Feng (2019) Formation of carbon–nitrogen bonds in carbon monoxide electrolysis. Nature Chemistry, 11 (9). pp. 846-851. ISSN 1755-4330. doi:10.1038/s41557-019-0312-z.

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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.

Item Type:Article
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URLURL TypeDescription ReadCube access
Jouny, Matthew0000-0002-5778-1106
Cheng, Tao0000-0003-4830-177X
Ko, Byung Hee0000-0002-0934-5182
Zhu, Jun-Jie0000-0002-8201-1285
Goddard, William A., III0000-0003-0097-5716
Jiao, Feng0000-0002-3335-3203
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.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FE0029868
Chinese Scholarship CouncilUNSPECIFIED
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-SC0012704
Subject Keywords:Chemical engineering; Electrocatalysis
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Issue or Number:9
Record Number:CaltechAUTHORS:20190620-142925725
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:96601
Deposited By: George Porter
Deposited On:23 Aug 2019 15:42
Last Modified:16 Nov 2021 17:22

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