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Formation of carbon–nitrogen bonds in carbon monoxide electrolysis


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. 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.

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Fig. 1: Acetamide production from CO electrolysis with NH3.
Fig. 2: The mechanism for CO reduction on Cu that shows how it splits at [*(HO)C=COH] into two pathways.
Fig. 3: Electrochemical production of longer amides from CO electrolysis in 5 M amine solutions.

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.


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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.

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Authors and Affiliations



F.J. conceived the idea and supervised the project. M.J. and J.J.-L. performed the electrolysis experiments, analysed the data and wrote the first draft of the manuscript. B.H.K. performed the SEM characterization. T.C. and W.A.G. performed the computational modelling studies. All the authors contributed to the discussion of the results and preparation of the manuscript. M.J., J.J.L. and T.C. have the right to list themselves first in the bibliographic documents.

Corresponding authors

Correspondence to William A. Goddard III or Feng Jiao.

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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.

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Supplementary Figs. 1–15, Tables 1–5 and Methods

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Jouny, M., Lv, JJ., Cheng, T. et al. Formation of carbon–nitrogen bonds in carbon monoxide electrolysis. Nat. Chem. 11, 846–851 (2019).

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