skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Univ. of Delaware, Newark, DE (United States)
  2. Univ. of Delaware, Newark, DE (United States); Nanjing Univ. (China)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States); Soochow Univ., Jiangsu (China)
  4. Nanjing Univ. (China)
  5. 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. 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., & 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 = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Closing the loop: captured CO 2 as a feedstock in the chemical industry
journal, January 2015

  • Otto, Alexander; Grube, Thomas; Schiebahn, Sebastian
  • Energy & Environmental Science, Vol. 8, Issue 11
  • DOI: 10.1039/C5EE02591E

Electrification and Decarbonization of the Chemical Industry
journal, September 2017


Climate change mitigation potential of carbon capture and utilization in the chemical industry
journal, May 2019

  • Kätelhön, Arne; Meys, Raoul; Deutz, Sarah
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 23
  • DOI: 10.1073/pnas.1821029116

Materials for solar fuels and chemicals
journal, December 2016

  • Montoya, Joseph H.; Seitz, Linsey C.; Chakthranont, Pongkarn
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4778

Terawatt-scale photovoltaics: Transform global energy
journal, May 2019


What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019


General Techno-Economic Analysis of CO 2 Electrolysis Systems
journal, February 2018

  • Jouny, Matthew; Luc, Wesley; Jiao, Feng
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 6
  • DOI: 10.1021/acs.iecr.7b03514

Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products
journal, March 2019


CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018


Insights into the Low Overpotential Electroreduction of CO 2 to CO on a Supported Gold Catalyst in an Alkaline Flow Electrolyzer
journal, November 2017


Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

  • Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
  • Nature, Vol. 508, Issue 7497
  • DOI: 10.1038/nature13249

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts
journal, July 2015

  • Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.
  • Journal of the American Chemical Society, Vol. 137, Issue 31
  • DOI: 10.1021/jacs.5b06227

Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper
journal, December 2015

  • Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide
  • Angewandte Chemie International Edition, Vol. 55, Issue 4
  • DOI: 10.1002/anie.201508851

Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products
journal, January 2018

  • Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
  • ACS Catalysis, Vol. 8, Issue 2
  • DOI: 10.1021/acscatal.7b03477

Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper
journal, February 2019


Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide
journal, October 2018


CO Electroreduction: Current Development and Understanding of Cu-Based Catalysts
journal, November 2018


Rethinking amide bond synthesis
journal, December 2011

  • Pattabiraman, Vijaya R.; Bode, Jeffrey W.
  • Nature, Vol. 480, Issue 7378
  • DOI: 10.1038/nature10702

Nitrogen gets radical
journal, April 2019


High-rate electroreduction of carbon monoxide to multi-carbon products
journal, August 2018


Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water
journal, October 2016

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08534

Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
  • DOI: 10.1073/pnas.1612106114

Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer
journal, June 2015


Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction Investigated with 18 O Labeling
journal, December 2017

  • Lum, Yanwei; Ager, Joel W.
  • Angewandte Chemie International Edition, Vol. 57, Issue 2
  • DOI: 10.1002/anie.201710590

Absence of Oxidized Phases in Cu under CO Reduction Conditions
journal, February 2019


Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate
journal, April 2019


Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
journal, July 2018

  • Lum, Yanwei; Cheng, Tao; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 140, Issue 30
  • DOI: 10.1021/jacs.8b03986

Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0
journal, November 2015

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02247

Electrochemical CO Reduction: A Property of the Electrochemical Interface
journal, December 2018

  • Bagger, Alexander; Arnarson, Logi; Hansen, Martin H.
  • Journal of the American Chemical Society, Vol. 141, Issue 4
  • DOI: 10.1021/jacs.8b08839

Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes
journal, June 2013

  • Calle-Vallejo, Federico; Koper, Marc T. M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 28
  • DOI: 10.1002/anie.201301470

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles
journal, March 2016


Catalytic amide formation from non-activated carboxylic acids and amines
journal, January 2014

  • Lundberg, Helena; Tinnis, Fredrik; Selander, Nicklas
  • Chem. Soc. Rev., Vol. 43, Issue 8
  • DOI: 10.1039/C3CS60345H

Ammonia synthesis from N 2 and H 2 O using a lithium cycling electrification strategy at atmospheric pressure
journal, January 2017

  • McEnaney, Joshua M.; Singh, Aayush R.; Schwalbe, Jay A.
  • Energy & Environmental Science, Vol. 10, Issue 7
  • DOI: 10.1039/C7EE01126A

Electrochemical Ammonia Synthesis and Ammonia Fuel Cells
journal, December 2018


Beyond fossil fuel–driven nitrogen transformations
journal, May 2018

  • Chen, Jingguang G.; Crooks, Richard M.; Seefeldt, Lance C.
  • Science, Vol. 360, Issue 6391
  • DOI: 10.1126/science.aar6611

Introductory Guide to Assembling and Operating Gas Diffusion Electrodes for Electrochemical CO 2 Reduction
journal, February 2019


Role of Surface Oxophilicity in Copper-Catalyzed Water Dissociation
journal, August 2018


Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper
journal, December 2015

  • Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide
  • Angewandte Chemie, Vol. 128, Issue 4
  • DOI: 10.1002/ange.201508851

    Works referencing / citing this record:

    Carbon monoxide electroreduction as an emerging platform for carbon utilization
    journal, December 2019