Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Enhancing acetate selectivity by coupling anodic oxidation to carbon monoxide electroreduction


Electrocatalytic conversion of carbon monoxide (CO) is being actively developed as a key component for tandem CO2 electrolysis. Great effort has been devoted to engineering CO reduction electrocatalysts for better multicarbon product selectivity. However, less work has focused on other performance parameters that are crucial for commercializing CO electrolysis, such as liquid product concentration and purity. Here, we present an internally coupled purification strategy to substantially improve the acetate concentration and purity in CO electrolysis. This strategy utilizes an alkaline-stable anion exchange membrane with high ethanol permeability and a selective ethanol partial oxidation anode to control the CO reduction product stream. We demonstrate stable 120-h continuous operation of the CO electrolyser at a current density of 200 mA cm−2 and a full-cell potential of <2.3 V, continuously producing a 1.9 M acetate product stream with a purity of 97.7%. The acetate stream was further improved to a concentration of 7.6 M at >99% purity by tuning the reaction conditions. Finally, a techno-economic analysis shows that a highly concentrated liquid product stream is essential to reduce the energy consumption of product separation.

This is a preview of subscription content, access via your institution

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Production of concentrated acetate streams via eCOR.
Fig. 2: Anodic impact on selectivity via the partial oxidation of alcohols.
Fig. 3: Membrane crossover rate influence on eCOR selectivity.
Fig. 4: Techno-economic assessment of recirculative acetate production.

Data availability

All data is available from the authors upon reasonable request. Source data are provided with this paper.


  1. Overa, S., Feric, T. G., Park, A. H. A. & Jiao, F. Tandem and hybrid processes for carbon dioxide utilization. Joule 5, 8–13 (2021).

    Article  Google Scholar 

  2. Bushuyev, O. S. et al. What should we make with CO2 and how can we make it? Joule 2, 825–832 (2018).

    Article  CAS  Google Scholar 

  3. Nitopi, S. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119, 7610–7672 (2019).

    Article  CAS  Google Scholar 

  4. Jeng, E. & Jiao, F. Investigation of CO2 single-pass conversion in a flow electrolyzer. React. Chem. Eng. 5, 1768–1775 (2020).

    Article  CAS  Google Scholar 

  5. Rabinowitz, J. A. & Kanan, M. W. The future of low-temperature carbon dioxide electrolysis depends on solving one basic problem. Nat. Commun. 11, 10–12 (2020).

    Article  Google Scholar 

  6. Cofell, E. R., Nwabara, U. O., Bhargava, S. S., Henckel, D. E. & Kenis, P. J. A. Investigation of electrolyte-dependent carbonate formation on gas diffusion electrodes for CO2 electrolysis. ACS Appl. Mater. Interfaces 13, 15132–15142 (2021).

    Article  CAS  Google Scholar 

  7. Li, Y. C. et al. CO2 electroreduction from carbonate electrolyte. ACS Energy Lett. 4, 1427–1431 (2019).

    Article  CAS  Google Scholar 

  8. Yan, Z., Hitt, J. L., Zeng, Z., Hickner, M. A. & Mallouk, T. E. Improving the efficiency of CO2 electrolysis by using a bipolar membrane with a weak-acid cation exchange layer. Nat. Chem. 13, 33–40 (2021).

    Article  CAS  Google Scholar 

  9. Huang, J. E. et al. CO2 electrolysis to multicarbon products in strong acid. Science 372, 1074–1078 (2021).

    Article  CAS  Google Scholar 

  10. Cuellar, N. S. R., Scherer, C. & Ka, B. Two-step electrochemical reduction of CO2 towards multi-carbon products at high current densities. J. CO2 Util. 36, 263–275 (2020).

    Article  Google Scholar 

  11. Ozden, A. et al. Cascade CO2 electroreduction enables efficient carbonate-free production of ethylene. Joule 5, 706–710 (2021).

    Article  CAS  Google Scholar 

  12. Ripatti, D. S., Veltman, T. R. & Kanan, M. W. Carbon monoxide gas diffusion electrolysis that produces concentrated C2 products with high single-pass conversion. Joule 3, 240–256 (2019).

    Article  CAS  Google Scholar 

  13. Jouny, M., Hutchings, G. S. & Jiao, F. Carbon monoxide electroreduction as an emerging platform for carbon utilization. Nat. Catal. 2, 1062–1070 (2019).

    Article  CAS  Google Scholar 

  14. Luc, W. et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat. Catal. 2, 423–430 (2019).

    Article  CAS  Google Scholar 

  15. 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).

    Article  CAS  Google Scholar 

  16. Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).

    Article  CAS  Google Scholar 

  17. Zhu, P. et al. Direct and continuous generation of pure acetic acid solutions via electrocatalytic carbon monoxide reduction. Proc. Natl Acad. Sci. USA 118, e2010868118 (2021).

    Article  CAS  Google Scholar 

  18. Monteiro, M. C. O. et al. Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution. Nat. Catal. 4, 654–662 (2021).

    Article  CAS  Google Scholar 

  19. Shin, H., Kentaro, H. & Jiao, F. Techno-economic assessment of low-temperature carbon dioxide electrolysis. Nat. Sustain. 4, 911–919 (2021).

    Article  Google Scholar 

  20. Zhu, P. & Wang, H. High-purity and high-concentration liquid fuels through CO2 electroreduction. Nat. Catal. 4, 943–951 (2021).

    Article  CAS  Google Scholar 

  21. Miller, M. & Bazylak, A. A review of polymer electrolyte membrane fuel cell stack testing. J. Power Sources 196, 601–613 (2011).

    Article  CAS  Google Scholar 

  22. Marx, N., Boulon, L., Gustin, F., Hissel, D. & Agbossou, K. A review of multi-stack and modular fuel cell systems: interests, application areas and on-going research activities. Int. J. Hydrog. Energy 39, 12101–12111 (2014).

    Article  CAS  Google Scholar 

  23. Selamet, Ö. F., Becerikli, F., Mat, M. D. & Kaplan, Y. Development and testing of a highly efficient proton exchange membrane (PEM) electrolyzer stack. Int. J. Hydrog. Energy 36, 11480–11487 (2011).

    Article  CAS  Google Scholar 

  24. Noh, S., Jeon, J. Y., Adhikari, S., Kim, Y. S. & Bae, C. Molecular engineering of hydroxide conducting polymers for anion exchange membranes in electrochemical energy conversion technology. Acc. Chem. Res. 52, 2745–2755 (2019).

    Article  CAS  Google Scholar 

  25. Sano, K. I., Uchida, H. & Wakabayashi, S. A new process for acetic acid production by direct oxidation of ethylene. Catal. Surv. Jpn 3, 55–60 (1999).

    Article  CAS  Google Scholar 

  26. Etzi Coller Pascuzzi, M., Man, A. J. W., Goryachev, A., Hofmann, J. P. & Hensen, E. J. M. Investigation of the stability of NiFe-(oxy)hydroxide anodes in alkaline water electrolysis under industrially relevant conditions. Catal. Sci. Technol. 10, 5593–5601 (2020).

    Article  CAS  Google Scholar 

  27. Scheres Firak, D., Rocha Ribeiro, R., de Liz, M. V. & Peralta-Zamora, P. Investigations on iron leaching from oxides and its relevance for radical generation during Fenton-like catalysis. Environ. Earth Sci. 77, 1–9 (2018).

    Article  CAS  Google Scholar 

  28. Heenen, H. H. et al. Mechanism for acetate formation in CO(2) reduction on Cu: selectivity trends with pH and nanostructuring derive from mass transport. Preprint at ChemRxiv (2021).

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

    Article  CAS  Google Scholar 

  30. Yuan, N., Jiang, Q., Li, J. & Tang, J. A review on non-noble metal based electrocatalysis for the oxygen evolution reaction. Arab. J. Chem. 13, 4294–4309 (2020).

    Article  CAS  Google Scholar 

  31. Lu, X. & Zhao, C. Electrodeposition of hierarchically structured three-dimensional nickel-iron electrodes for efficient oxygen evolution at high current densities. Nat. Commun. 6, 6616 (2015).

    Article  CAS  Google Scholar 

  32. Lees, E. W., Mowbray, B. A. W., Parlane, F. G. L. & Berlinguetter, C. P. Gas diffusion electrodes and membranes for CO2 reduction electrolyzers. Nat. Rev. Mater. 7, 55–64 (2022).

    Article  CAS  Google Scholar 

  33. 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).

    Article  CAS  Google Scholar 

  34. Ramdin, M. et al. Electroreduction of CO2/CO to C2 products: process modeling, downstream separation, system integration, and economic analysis. Ind. Eng. Chem. Res. 60, 17862–17880 (2021).

    Article  CAS  Google Scholar 

  35. Luc, W., Rosen, J. & Jiao, F. An Ir-based anode for a practical CO2 electrolyzer. Catal. Today 288, 79–84 (2017).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

Download references


This material is based upon work supported by the US Department of Energy under Award Number DE-FE0031910.

Author information

Authors and Affiliations



S.O. conducted the experiments, performed the data analysis and wrote the first draft of the manuscript. B.S.C. conducted the techno-economic analysis. B.S. and D.T. produced and conducted the analysis of the anion exchange membrane. B.H.K. performed the XPS measurements and analysed the XPS data. H.S. conducted the scanning electron microscopy measurements. C.B. supervised the synthesis of the anion exchange membranes. F.J. revised the manuscript and supervised the whole project. All authors commented on the final version of the manuscript.

Corresponding author

Correspondence to Feng Jiao.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Notes 1–5, Figs. 1–43 and Tables 1–8.

Source data

Source Data Fig. 1

Data for 120-h durability in Fig. 1b.

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Overa, S., Crandall, B.S., Shrimant, B. et al. Enhancing acetate selectivity by coupling anodic oxidation to carbon monoxide electroreduction. Nat Catal 5, 738–745 (2022).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing