Skip to main content

Thank you for visiting nature.com. 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.

  • Article
  • Published:

Recoverable operation strategy for selective and stable electrochemical carbon dioxide reduction to methane

Nature Energy volume 10, pages 1360–1370 (2025) Cite this article

Subjects

Abstract

In the carbon dioxide (CO2) electroreduction reaction, catalysts determine, to a large extent, the system’s product selectivity, energy efficiency and stability. Conventionally, catalysts are prepared and optimized ex situ before the reaction, but they often suffer from low stability due to intrinsic structural changes during the reaction. Here we demonstrate a recoverable operation strategy for selective and stable electroreduction of CO2 to methane. In this approach, active catalysts are formed and fully reset in situ during CO2 electroreduction reaction. By stabilizing catalyst precursors and controlling the formation and removal of the catalysts, we demonstrate an over 500-hour CO2-to-methane conversion with a Faradaic efficiency of over 60% at the reduction current density of above 0.2 A cm−2 and full-cell voltage of below 4.0 V. We further showcase benefits of the recoverable operation for potential integration with intermittent renewable power supply, contributing to more than 100 days with day-on and night-off operation.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic illustration of the CO2 to hydrocarbon conversion process using different strategies.
The alternative text for this image may have been generated using AI.
Fig. 2: Proof of concept of the recoverable operation in a conventional H-cell configuration.
The alternative text for this image may have been generated using AI.
Fig. 3: In situ characterization of the catalysts under recoverable operation.
The alternative text for this image may have been generated using AI.
Fig. 4: Performance demonstration in a BPM-MEA cell configuration.
The alternative text for this image may have been generated using AI.
Fig. 5: Effect of Py-Cu2+ complex for improved stability performance in BPM-MEA system.
The alternative text for this image may have been generated using AI.
Fig. 6: Long-term stability demonstration with improved energy efficiency in CEM-MEA system.
The alternative text for this image may have been generated using AI.

Similar content being viewed by others

Data availability

All the data supporting the findings of this study are available within the article and its Supplementary Information and Source Data file. Source data are provided with this paper.

References

  1. Kibria, M. G. et al. Electrochemical CO2 reduction into chemical feedstocks: from mechanistic electrocatalysis models to system design. Adv. Mater. 31, 1807166 (2019).

    Article  Google Scholar 

  2. Belsa, B. et al. Materials challenges on the path to gigatonne CO2 electrolysis. Nat. Rev. Mater. 9, 535–549 (2024).

    Article  Google Scholar 

  3. Wu, Y. et al. Heterogeneous electrocatalysis of carbon dioxide to methane. Methane 2, 148–175 (2023).

    Article  Google Scholar 

  4. Medina, O. E., Amell, A. A., López, D. & Santamaría, A. Comprehensive review of nickel-based catalysts advancements for CO2 methanation. Renew. Sustain. Energy Rev. 207, 114926 (2025).

    Article  Google Scholar 

  5. Liu, Z. H. et al. Recent advances in thermal catalytic CO2 methanation on hydrotalcite-derived catalysts. Fuel 321, 124115 (2022).

    Article  Google Scholar 

  6. Wang, R. & Jin, S. Flexible participation of electrosynthesis in dynamic electricity markets. Nat. Energy 9, 1062–1063 (2024).

    Google Scholar 

  7. Samu, A. A. et al. Intermittent operation of CO2 electrolyzers at industrially relevant current densities. ACS Energy Lett. 7, 1859–1861 (2022).

    Article  Google Scholar 

  8. Zhang, H., Liang, Q. & Xie, K. How to rationally design homogeneous catalysts for efficient CO2 electroreduction? iScience 27, 108973 (2024).

    Article  Google Scholar 

  9. Xue, Y., Guo, Y., Cui, H. & Zhou, Z. Catalyst design for electrochemical reduction of CO2 to multicarbon products. Small Methods 5, 2100736 (2021).

    Article  Google Scholar 

  10. Zhu, S. et al. Recent advances in catalyst structure and composition engineering strategies for regulating CO2 electrochemical reduction. Adv. Mater. 33, 2005484 (2021).

    Article  Google Scholar 

  11. Chen, J. & Wang, L. Effects of the catalyst dynamic changes and influence of the reaction environment on the performance of electrochemical CO2 reduction. Adv. Mater. 34, 2103900 (2022).

    Article  Google Scholar 

  12. Lai, W., Qiao, Y., Wang, Y. & Huang, H. Stability issues in electrochemical CO2 reduction: recent advances in fundamental understanding and design strategies. Adv. Mater. 35, 2306288 (2023).

    Article  Google Scholar 

  13. Lee, S. H. et al. Oxidation state and surface reconstruction of Cu under CO2 reduction conditions from in situ X-ray characterization. J. Am. Chem. Soc. 143, 588–592 (2021).

    Article  Google Scholar 

  14. Vavra, J., Shen, T.-H., Stoian, D., Tileli, V. & Buonsanti, R. Real-time monitoring reveals dissolution/redeposition mechanism in copper nanocatalysts during the initial stages of the CO2 reduction reaction. Angew. Chem. Int. Ed. 60, 1347–1354 (2021).

    Article  Google Scholar 

  15. Grosse, P. et al. Dynamic transformation of cubic copper catalysts during CO2 electroreduction and its impact on catalytic selectivity. Nat. Commun. 12, 6736 (2021).

    Article  Google Scholar 

  16. Tomc, B. et al. Deactivation of copper electrocatalysts during CO2 reduction occurs via dissolution and selective redeposition mechanism. J. Mater. Chem. A 13, 4119–4128 (2025).

    Article  Google Scholar 

  17. Lee, S. H. et al. Structural transformation and degradation of Cu oxide nanocatalysts during electrochemical CO2 reduction. J. Am. Chem. Soc. 147, 6536–6548 (2025).

    Article  Google Scholar 

  18. Li, F. et al. Interplay of electrochemical and electrical effects induces structural transformations in electrocatalysts. Nat. Catal. 4, 479–487 (2021).

    Article  Google Scholar 

  19. Okatenko, V. et al. Alloying as a strategy to boost the stability of copper nanocatalysts during the electrochemical CO2 reduction reaction. J. Am. Chem. Soc. 145, 5370–5383 (2023).

    Article  Google Scholar 

  20. Zhang, Z. et al. ‘Two ships in a bottle’ design for Zn–Ag–O catalyst enabling selective and long-lasting CO2 electroreduction. J. Am. Chem. Soc. 143, 6855–6864 (2021).

    Article  Google Scholar 

  21. Ko, Y.-J. et al. Exploring dopant effects in stannic oxide nanoparticles for CO2 electro-reduction to formate. Nat. Commun. 13, 2205 (2022).

    Article  Google Scholar 

  22. Tan, X. et al. Stabilizing copper by a reconstruction-resistant atomic Cu–O–Si interface for electrochemical CO2 reduction. J. Am. Chem. Soc. 145, 8656–8664 (2023).

    Article  Google Scholar 

  23. Levchenko, T. I. et al. Electrocatalytic CO2 reduction with atomically precise Au13 nanoclusters: effect of ligand shell on catalytic performance. ACS Catal. 14, 4155–4163 (2024).

    Article  Google Scholar 

  24. Kim, J.-Y. et al. Quasi-graphitic carbon shell-induced Cu confinement promotes electrocatalytic CO2 reduction toward C2+ products. Nat. Commun. 12, 3765 (2021).

    Article  Google Scholar 

  25. Thevenon, A., Rosas-Hernández, A., Peters, J. C. & Agapie, T. In-situ nanostructuring and stabilization of polycrystalline copper by an organic salt additive promotes electrocatalytic CO2 reduction to ethylene. Angew. Chem. Int. Ed. 58, 16952–16958 (2019).

    Article  Google Scholar 

  26. Han, Z. et al. Steering surface reconstruction of copper with electrolyte additives for CO2 electroreduction. Nat. Commun. 13, 3158 (2022).

    Article  Google Scholar 

  27. Guntern, Y. T. et al. Nanocrystal/metal–organic framework hybrids as electrocatalytic platforms for CO2 conversion. Angew. Chem. Int. Ed. 58, 12632–12639 (2019).

    Article  Google Scholar 

  28. Guo, S.-T. et al. Stabilizing undercoordinated Zn active sites through confinement in CeO2 nanotubes for efficient electrochemical CO2 reduction. Angew. Chem. Int. Ed. 63, e202314099 (2024).

    Article  Google Scholar 

  29. Xue, J. et al. Turning copper into an efficient and stable CO evolution catalyst beyond noble metals. Nat. Commun. 15, 5998 (2024).

    Article  Google Scholar 

  30. Albertini, P. P. et al. Hybrid oxide coatings generate stable Cu catalysts for CO2 electroreduction. Nat. Mater. 23, 680–687 (2024).

    Article  Google Scholar 

  31. Xu, Y. et al. Low coordination number copper catalysts for electrochemical CO2 methanation in a membrane electrode assembly. Nat. Commun. 12, 2932 (2021).

    Article  Google Scholar 

  32. Chen, S. et al. Engineering water molecules activation center on multisite electrocatalysts for enhanced CO2 methanation. J. Am. Chem. Soc. 144, 12807–12815 (2022).

    Article  Google Scholar 

  33. Fan, Q. et al. Manipulating Cu nanoparticle surface oxidation states tunes catalytic selectivity toward CH4 or C2+ products in CO2 electroreduction. Adv. Energy Mater. 11, 2101424 (2021).

    Article  Google Scholar 

  34. Su, X. et al. Complementary operando spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol. Nat. Commun. 13, 1322 (2022).

    Article  Google Scholar 

  35. Wang, J. et al. In situ X-ray spectroscopies beyond conventional X-ray absorption spectroscopy on deciphering dynamic configuration of electrocatalysts. Nat. Commun. 14, 6576 (2023).

    Article  Google Scholar 

  36. Du, Z.-Y. et al. In situ Raman spectroscopic studies of electrochemical CO2 reduction on Cu-based electrodes. J. Phys. Chem. C 128, 11741–11755 (2024).

    Article  Google Scholar 

  37. Zhan, C. et al. Key intermediates and Cu active sites for CO2 electroreduction to ethylene and ethanol. Nat. Energy 9, 1485–1496 (2024).

    Article  Google Scholar 

  38. Du, Z.-Y. et al. Promoting water activation via molecular engineering enables efficient asymmetric C–C coupling during CO2 electroreduction. J. Am. Chem. Soc. 146, 32870–32879 (2024).

    Article  Google Scholar 

  39. Obasanjo, C. A. et al. High-rate and selective conversion of CO2 from aqueous solutions to hydrocarbons. Nat. Commun. 14, 3176 (2023).

    Article  Google Scholar 

  40. Lee, G. et al. CO2 electroreduction to multicarbon products from carbonate capture liquid. Joule 7, 1277–1288 (2023).

    Article  Google Scholar 

  41. Singh, D. P., Ojha, A. K. & Srivastava, O. N. Synthesis of different Cu(OH)2 and CuO (nanowires, rectangles, seed-, belt-, and sheetlike) nanostructures by simple wet chemical route. J. Phys. Chem. C 113, 3409–3418 (2009).

    Article  Google Scholar 

  42. Bowmaker, G. A. et al. Mechanochemical synthesis in copper(ii) halide/pyridine systems: single crystal X-ray diffraction and IR spectroscopic studies. Dalton Trans. 40, 5102–5115 (2011).

    Article  Google Scholar 

  43. Satyanarayan, P. in Pyridine: A Useful Ligand in Transition Metal Complexes (ed. Parashar, P. P.) Ch. 5 (IntechOpen, 2018).

  44. Tian, Z.-Q. & Ren, B. Adsorption and reaction at electrochemical interfaces as probed by surface-enhanced raman spectroscopy. Annu. Rev. Phys. Chem. 55, 197–229 (2004).

    Article  Google Scholar 

  45. Petrov, K. V. et al. Bipolar membranes for intrinsically stable and scalable CO2 electrolysis. Nat. Energy 9, 932–938 (2024).

    Article  Google Scholar 

  46. Blommaert, M. A. et al. Insights and challenges for applying bipolar membranes in advanced electrochemical energy systems. ACS Energy Lett. 6, 2539–2548 (2021).

    Article  Google Scholar 

  47. Nourmohammadi Khiarak, B. et al. Macro- and nano-porous ag electrodes enable selective and stable aqueous CO2 reduction. Small 21, 2409669 (2025).

    Article  Google Scholar 

  48. King, H. J. et al. Photon-induced, timescale, and electrode effects critical for the in situ X-ray spectroscopic analysis of electrocatalysts: the water oxidation case. J. Phys. Chem. C 123, 28533–28549 (2019).

    Article  Google Scholar 

  49. Ramadhany, P. et al. Triggering C‒N coupling on metal oxide nanocomposite for the electrochemical reduction of CO2 and \({\mathrm{NO}}_{{x}^{-}}\) to formamide. Adv. Energy Mater. 14, 2401786 (2024).

    Article  Google Scholar 

  50. Tran-Phu, T. et al. Understanding the role of (W, Mo, Sb) dopants in the catalyst evolution and activity enhancement of Co3O4 during water electrolysis via in situ spectroelectrochemical techniques. Small 19, 2208074 (2023).

    Article  Google Scholar 

Download references

Acknowledgements

C.-T.D. acknowledges the financial support from the Canada Research Chairs Program, the Natural Sciences and Engineering Research Council of Canada (NSERC), Canada Foundation for Innovation (CFI) and Queen’s University. V.G. and F.P.G.d.A. are thankful to PID2022-138127NA-I00 and CEX2019-000910-S (MCIN/AEI/10.13039/501100011033), Fundació Cellex, Fundació Mir-Puig, Generalitat de Catalunya through CERCA and the European Union (NASCENT, 101077243). G.T.S.T.d.S. acknowledges funding from FAPESP (#2023/10268-2 and #2013/07296-2). This research used resources of the Advanced Photon Source (beamline 12-BM), a US Department of Energy (DOE) Office of Science User Facilities, operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357 and the Australian Synchrotron part of ANSTO via proposal M23234. R.K.H. is grateful for an Australian research council future fellowship FT230100054.

Author information

Author notes

  1. These authors contributed equally: Guorui Gao, Behnam Nourmohammadi Khiarak, Hengzhou Liu.

Authors and Affiliations

  1. Department of Chemical Engineering, Queen’s University, Kingston, Ontario, Canada

    Guorui Gao, Behnam Nourmohammadi Khiarak, Cornelius A. Obasanjo, Hung D. T. Lai, Gelson T. S. T. da Silva & Cao-Thang Dinh

  2. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Hengzhou Liu, Jiantao Li, Huajie Ze, John Weiss, Zedong Zhang & Edward H. Sargent

  3. School of Science, Computing and Emerging Technologies, Swinburne University of Technology, Melbourne, Victoria, Australia

    Thành Trần-Phú & Rosalie K. Hocking

  4. Department of Mechanical and Materials Engineering, Queen’s University, Kingston, Ontario, Canada

    Jackson Crane

  5. Interdisciplinary Laboratory of Electrochemistry and Ceramics, Department of Chemistry, Federal University of Sao Carlos, São Carlos, Brazil

    Gelson T. S. T. da Silva

  6. ICFO–Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, Barcelona, Spain

    Viktoria Golovanova & F. Pelayo García de Arquer

  7. X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Sungsik Lee

Authors
  1. Guorui Gao
    View author publications

    Search author on:PubMed Google Scholar

  2. Behnam Nourmohammadi Khiarak
    View author publications

    Search author on:PubMed Google Scholar

  3. Hengzhou Liu
    View author publications

    Search author on:PubMed Google Scholar

  4. Thành Trần-Phú
    View author publications

    Search author on:PubMed Google Scholar

  5. Cornelius A. Obasanjo
    View author publications

    Search author on:PubMed Google Scholar

  6. Jackson Crane
    View author publications

    Search author on:PubMed Google Scholar

  7. Hung D. T. Lai
    View author publications

    Search author on:PubMed Google Scholar

  8. Gelson T. S. T. da Silva
    View author publications

    Search author on:PubMed Google Scholar

  9. Viktoria Golovanova
    View author publications

    Search author on:PubMed Google Scholar

  10. Jiantao Li
    View author publications

    Search author on:PubMed Google Scholar

  11. Huajie Ze
    View author publications

    Search author on:PubMed Google Scholar

  12. John Weiss
    View author publications

    Search author on:PubMed Google Scholar

  13. Zedong Zhang
    View author publications

    Search author on:PubMed Google Scholar

  14. Sungsik Lee
    View author publications

    Search author on:PubMed Google Scholar

  15. Rosalie K. Hocking
    View author publications

    Search author on:PubMed Google Scholar

  16. F. Pelayo García de Arquer
    View author publications

    Search author on:PubMed Google Scholar

  17. Edward H. Sargent
    View author publications

    Search author on:PubMed Google Scholar

  18. Cao-Thang Dinh
    View author publications

    Search author on:PubMed Google Scholar

Contributions

C.-T.D. and E.H.S. supervised the project. G.G., B.N.K., C.A.O. and C.-T.D. designed all experiments. G.G., B.N.K., C.A.O. and H.D.T.L. conducted the experiments and data processing. H.L., J.L., Z.Z. and S.L. performed ex situ XAS analysis. H.L. and J.W. performed XPS analysis. H.L. and H.Z. performed in situ Raman analysis. T.T.-P. and R.K.H. performed in situ XAS experiments and analyses. G.T.S.T.d.S., G.G., B.N.K., V.G. and F.P.G.d.A. performed SEM analysis. J.C. performed multiphysics modelling. G.G., B.N.K., H.L., C.A.O. and H.D.T.L. wrote the draft of the manuscript. All authors discussed the results and assisted during manuscript preparation.

Corresponding authors

Correspondence to Edward H. Sargent or Cao-Thang Dinh.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Maximilian Fleischer, Chanyeon Kim and the other, anonymous, reviewer 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 (download PDF )

Supplementary Notes 1–7, Figs. 1–54, Tables 1 and 2 and refs. 1–16.

Supplementary Data 1 (download XLSX )

Source data for supplementary figures.

Supplementary Data 2 (download XLSX )

Source data for supplementary figures.

Supplementary Data 3 (download XLSX )

Source data for supplementary figures.

Supplementary Data 4 (download XLSX )

Source data for supplementary figures.

Supplementary Data 5 (download XLSX )

Source data for supplementary figures.

Source data

Source Data Fig. 2 (download XLSX )

Statistical source data.

Source Data Fig. 3 (download XLSX )

Statistical source data.

Source Data Fig. 4 (download XLSX )

Statistical source data.

Source Data Fig. 5 (download XLSX )

Statistical source data.

Source Data Fig. 6 (download XLSX )

Statistical source data.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) 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

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, G., Khiarak, B.N., Liu, H. et al. Recoverable operation strategy for selective and stable electrochemical carbon dioxide reduction to methane. Nat Energy 10, 1360–1370 (2025). https://doi.org/10.1038/s41560-025-01883-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41560-025-01883-w

This article is cited by

Search

Advanced search

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