Article | Published:

High-rate electroreduction of carbon monoxide to multi-carbon products

Nature Catalysisvolume 1pages748755 (2018) | Download Citation


Carbon monoxide electrolysis has previously been reported to yield enhanced multi-carbon (C2+) Faradaic efficiencies of up to ~55%, but only at low reaction rates. This is due to the low solubility of CO in aqueous electrolytes and operation in batch-type reactors. Here, we present a high-performance CO flow electrolyser with a well controlled electrode–electrolyte interface that can reach total current densities of up to 1 A cm–2, together with improved C2+ selectivities. Computational transport modelling and isotopic C18O reduction experiments suggest that the enhanced activity is due to a higher surface pH under CO reduction conditions, which facilitates the production of acetate. At optimal operating conditions, we achieve a C2+ Faradaic efficiency of ~91% with a C2+ partial current density over 630 mA cm–2. Further investigations show that maintaining an efficient triple-phase boundary at the electrode–electrolyte interface is the most critical challenge in achieving a stable CO/CO2 electrolysis process at high rates.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Change history

  • 15 November 2018

    The original Supplementary Information file published with this Article had the diffusion coefficient values of carbonate and hydrogen carbonate ions switched in the table below equation (21). A new Supplementary Information file has been uploaded with the correct values.


  1. 1.

    Haegel, N. M. et al. Terawatt-scale photovoltaics: trajectories and challenges. Science 356, 141–143 (2017).

  2. 2.

    Herron, J. A., Kim, J., Upadhye, A. A., Huber, G. W. & Maravelias, C. T. A general framework for the assessment of solar fuel technologies. Energy Environ. Sci. 8, 126–157 (2015).

  3. 3.

    Whipple, D. T. & Kenis, P. J. Prospects of CO2 utilization via direct heterogeneous electrochemical reduction. J. Phys. Chem. Lett. 1, 3451–3458 (2010).

  4. 4.

    Gu, S., Xu, B. & Yan, Y. Electrochemical energy engineering: a new frontier of chemical engineering innovation. Annu. Rev. Chem. Biomol. Eng. 5, 429–454 (2014).

  5. 5.

    Martín, A. J., Larrazábal, G. O. & Pérez-Ramírez, J. Towards sustainable fuels and chemicals through the electrochemical reduction of CO2: lessons from water electrolysis. Green Chem. 17, 5114–5130 (2015).

  6. 6.

    Jouny, M., Luc, W. & Jiao, F. General techno-economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).

  7. 7.

    Jhong, H.-R. M., Ma, S. & Kenis, P. J. A. Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities. Curr. Opin. Chem. Eng. 2, 191–199 (2013).

  8. 8.

    Liu, X. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 15438 (2017).

  9. 9.

    Montoya, J. H., Shi, C., Chan, K. & Norskov, J. K. Theoretical insights into a CO dimerization mechanism in CO2 electroreduction. J. Phys. Chem. Lett. 6, 2032–2037 (2015).

  10. 10.

    Huang, Y., Handoko, A. D., Hirunsit, P. & Yeo, B. S. Electrochemical reduction of CO2 using copper single-crystal surfaces: effects of CO* coverage on the selective formation of ethylene. ACS Catal. 7, 1749–1756 (2017).

  11. 11.

    Verma, S., Lu, X., Ma, S., Masel, R. I. & Kenis, P. J. A. The effect of electrolyte composition on the electroreduction of CO2 to CO on Ag based gas diffusion electrodes. Phys. Chem. Chem. Phys. 18, 7075–7084 (2016).

  12. 12.

    Xiao, H., Cheng, T., Goddard, W. A. III & Sundararaman, R. Mechanistic explanation of the pH dependence and onset potentials for hydrocarbon products from electrochemical reduction of CO on Cu (111). J. Am. Chem. Soc. 138, 483–486 (2016).

  13. 13.

    Dinh, C.-T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).

  14. 14.

    Verma, S. et al. Insights into the low overpotential electroreduction of CO2 to CO on a supported gold catalyst in an alkaline flow electrolyzer. ACS Energy Lett. 3, 193–198 (2018).

  15. 15.

    Spurgeon, J. M. & Kumar, B. A comparative technoeconomic analysis of pathways for commercial electrochemical CO2 reduction to liquid products. Energy Environ. Sci. 11, 1536–1551 (2018).

  16. 16.

    Reske, R., Mistry, H., Behafarid, F., Roldan Cuenya, B. & Strasser, P. Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles. J. Am. Chem. Soc. 136, 6978–6986 (2014).

  17. 17.

    Loiudice, A. et al. Tailoring copper nanocrystals towards C2 products in electrochemical CO2 reduction. Angew. Chem. Int. Ed. 55, 5789–5792 (2016).

  18. 18.

    Baturina, O. A. et al. CO2 electroreduction to hydrocarbons on carbon-supported Cu nanoparticles. ACS Catal. 4, 3682–3695 (2014).

  19. 19.

    Kas, R. et al. Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction. Nat. Commun. 7, 10748 (2016).

  20. 20.

    Sen, S., Liu, D. & Palmore, G. T. R. Electrochemical reduction of CO2 at copper nanofoams. ACS Catal. 4, 3091–3095 (2014).

  21. 21.

    Rahaman, M., Dutta, A., Zanetti, A. & Broekmann, P. Electrochemical reduction of CO2 into multicarbon alcohols on activated Cu mesh catalysts: an identical location (IL) study. ACS Catal. 7, 7946–7956 (2017).

  22. 22.

    Dutta, A., Rahaman, M., Luedi, N. C., Mohos, M. & Broekmann, P. Morphology matters: tuning the product distribution of CO2 electroreduction on oxide-derived Cu foam catalysts. ACS Catal. 6, 3804–3814 (2016).

  23. 23.

    Hahn, C. et al. Engineering Cu surfaces for the electrocatalytic conversion of CO2: controlling selectivity toward oxygenates and hydrocarbons. Proc. Natl Acad. Sci. USA 114, 5918–5923 (2017).

  24. 24.

    Kim, Y.-G., Javier, A., Baricuatro, J. H. & Soriaga, M. P. Regulating the product distribution of CO reduction by the atomic-level structural modification of the Cu electrode surface. Electrocatalysis 7, 391–399 (2016).

  25. 25.

    Clark, E. L., Hahn, C., Jaramillo, T. F. & Bell, A. T. Electrochemical CO2 reduction over compressively strained CuAg surface alloys with enhanced multi-carbon oxygenate selectivity. J. Am. Chem. Soc. 139, 15848–15857 (2017).

  26. 26.

    Ren, D., Ang, B. S.-H. & Yeo, B. S. Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts. ACS Catal. 6, 8239–8247 (2016).

  27. 27.

    Zhang, S. et al. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane. Proc. Natl Acad. Sci. USA 112, 15809–15814 (2015).

  28. 28.

    Sarfraz, S., Garcia-Esparza, A. T., Jedidi, A., Cavallo, L. & Takanabe, K. Cu–Sn bimetallic catalyst for selective aqueous electroreduction of CO2 to CO. ACS Catal. 6, 2842–2851 (2016).

  29. 29.

    Lee, S., Park, G. & Lee, J. Importance of Ag–Cu biphasic boundaries for selective electrochemical reduction of CO2 to ethanol. ACS Catal. 7, 8594–8604 (2017).

  30. 30.

    Mistry, H. et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016).

  31. 31.

    Jiang, K. et al. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 1, 111–119 (2018).

  32. 32.

    Gao, D. et al. Plasma-activated copper nanocube catalysts for efficient carbon dioxide electroreduction to hydrocarbons and alcohols. ACS Nano 11, 4825–4831 (2017).

  33. 33.

    Handoko, A. D. et al. Mechanistic insights into the selective electroreduction of carbon dioxide to ethylene on Cu2O-derived copper catalysts. J. Phys. Chem. C 120, 20058–20067 (2016).

  34. 34.

    Tang, W. et al. The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction. Phys. Chem. Chem. Phys. 14, 76–81 (2012).

  35. 35.

    Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).

  36. 36.

    Bertheussen, E. et al. Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide‐derived copper. Angew. Chem. Int. Ed. 55, 1450–1454 (2016).

  37. 37.

    Raciti, D. et al. Low-overpotential electroreduction of carbon monoxide using copper nanowires. ACS Catal. 7, 4467–4472 (2017).

  38. 38.

    Feng, X., Jiang, K., Fan, S. & Kanan, M. W. A direct grain-boundary–activity correlation for CO electroreduction on Cu nanoparticles. ACS Cent. Sci. 2, 169–174 (2016).

  39. 39.

    Verdaguer-Casadevall, A. et al. Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts. J. Am. Chem. Soc. 137, 9808–9811 (2015).

  40. 40.

    Mariano, R. G., McKelvey, K., White, H. S. & Kanan, M. W. Selective increase in CO2 electroreduction activity at grain-boundary surface terminations. Science 358, 1187–1192 (2017).

  41. 41.

    Raciti, D. & Wang, C. Recent advances in CO2 reduction electrocatalysis on copper. ACS Energy Lett. 3, 1545–1556 (2018).

  42. 42.

    Eren, B. et al. Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption. Science 351, 475–478 (2016).

  43. 43.

    Eren, B. et al. One-dimensional nanoclustering of the Cu(100) surface under CO gas in the mbar pressure range. Surf. Sci. 651, 210–214 (2016).

  44. 44.

    Gunathunge, C. M. et al. Spectroscopic observation of reversible surface reconstruction of copper electrodes under CO2 reduction. J. Phys. Chem. C 121, 12337–12344 (2017).

  45. 45.

    Kuhl, K. P., Cave, E. R., Abram, D. N. & Jaramillo, T. F. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ. Sci. 5, 7050–7059 (2012).

  46. 46.

    Gupta, N., Gattrell, M. & MacDougall, B. Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions. J. Appl. Electrochem. 36, 161–172 (2006).

  47. 47.

    Ma, S. et al. Carbon nanotube containing Ag catalyst layers for efficient and selective reduction of carbon dioxide. J. Mater. Chem. A 4, 8573–8578 (2016).

  48. 48.

    Hoang, T. T. H., Ma, S., Gold, J. I., Kenis, P. J. A. & Gewirth, A. A. Nanoporous copper films by additive-controlled electrodeposition: CO2 reduction catalysis. ACS Catal. 7, 3313–3321 (2017).

  49. 49.

    Birdja, Y. Y. & Koper, M. T. The importance of Cannizzaro-type reactions during electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 139, 2030–2034 (2017).

  50. 50.

    Garza, A. J., Bell, A. T. & Head-Gordon, M. Mechanism of CO2 reduction at copper surfaces: pathways to C2 products. ACS Catal. 8, 1490–1499 (2018).

  51. 51.

    Greenzaid, P., Luz, Z. & Samuel, D. A nuclear magnetic resonance study of the reversible hydration of aliphatic aldehydes and ketones. II. The acid-catalyzed oxygen exchange of acetaldehyde. J. Am. Chem. Soc. 89, 756–759 (1967).

  52. 52.

    Clark, E. L. & Bell, A. T. Direct observation of the local reaction environment during the electrochemical reduction of CO2. J. Am. Chem. Soc. 140, 7012–7020 (2018).

  53. 53.

    Gileadi, E. Physical Electrochemistry: Fundamentals, Techniques and Applications (Wiley-VCH, Weinheim, 2011).

  54. 54.

    Hori, Y., Takahashi, I., Koga, O. & Hoshi, N. Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes. J. Mol. Catal. A 199, 39–47 (2003).

  55. 55.

    Song, Y. et al. High-selectivity electrochemical conversion of CO2 to ethanol using a copper nanoparticle/N-doped graphene electrode. ChemistrySelect 1, 6055–6061 (2016).

  56. 56.

    Ren, D. et al. Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper(I) oxide catalysts. ACS Catal. 5, 2814–2821 (2015).

  57. 57.

    Weng, Z. et al. Electrochemical CO2 reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution. J. Am. Chem. Soc. 138, 8076–8079 (2016).

  58. 58.

    De Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).

  59. 59.

    Hoang, T. T. H. et al. Nanoporous copper–silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791–5797 (2018).

  60. 60.

    Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

Download references


We thank B. Xu and M. Dunwell for useful discussion. We also thank B. Murphy for help with the GC–MS experiments and B. Setzler for help with the transport model. This material is based on work supported by the Department of Energy under award number DE-FE0029868. The authors also thank the National Science Foundation Faculty Early Career Development Program (award number CBET-1350911). This research used resources of the Advanced Photon Source, a US Department of Energy Office of Science user facility operated for the Department of Energy Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357.

Author information


  1. Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    • Matthew Jouny
    • , Wesley Luc
    •  & Feng Jiao


  1. Search for Matthew Jouny in:

  2. Search for Wesley Luc in:

  3. Search for Feng Jiao in:


M.J. synthesized the electrodes, performed the XAS characterization, designed and performed the flow electrolysis experiments, analysed the data, and wrote the manuscript. W.L. performed the SEM, XPS and XRD characterizations, and surface pH calculations. F.J. supervised the project. All authors contributed to discussion of the results and manuscript preparation.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Feng Jiao.

Supplementary information

  1. Supplementary Information

    Supplementary Methods, Supplementary Figures 1–16, Supplementary Tables 1 and 2, Supplementary References

About this article

Publication history




Issue Date


Further reading