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.

Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4

Abstract

Electrochemical CO2 reduction to value-added chemical feedstocks is of considerable interest for renewable energy storage and renewable source generation while mitigating CO2 emissions from human activity. Copper represents an effective catalyst in reducing CO2 to hydrocarbons or oxygenates, but it is often plagued by a low product selectivity and limited long-term stability. Here we report that copper nanowires with rich surface steps exhibit a remarkably high Faradaic efficiency for C2H4 that can be maintained for over 200 hours. Computational studies reveal that these steps are thermodynamically favoured compared with Cu(100) surface under the operating conditions and the stepped surface favours C2 products by suppressing the C1 pathway and hydrogen production.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Schematic of preparing CuNWs with surface steps.
Fig. 2: TEM characterizations of the Syn-CuNW and A-CuNW.
Fig. 3: Electrochemical characterization of the surfaces of the CuNWs.
Fig. 4: Electrochemical CO2RR performance.
Fig. 5: The stability and activity of the Cu(511) step surface.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

References

  1. 1.

    Schreier, M. et al. Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2, 17087 (2017).

    CAS  Google Scholar 

  2. 2.

    Hori, Y., Wakebe, H., Tsukamoto, T. & Koga, O. Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media. Electrochim. Acta 39, 1833–1839 (1994).

    CAS  Google Scholar 

  3. 3.

    Hori, Y., Kikuchi, K. & Suzuki, S. Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogen carbonate solution. Chem. Lett. 14, 1695–1698 (1985).

    Google Scholar 

  4. 4.

    Qiao, J., Liu, Y., Hong, F. & Zhang, J. A review of catalysts for the electro-reduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 43, 631–675 (2014).

    CAS  PubMed  Google Scholar 

  5. 5.

    Gawande, M. B. et al. Cu and Cu-based nanoparticles: synthesis and applications in catalysis. Chem. Rev. 116, 3722–3811 (2016).

    CAS  Google Scholar 

  6. 6.

    Kim, D., Resasco, J., Yu, Y., Asiri, A. M. & Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat. Commun. 5, 4948 (2014).

    CAS  Google Scholar 

  7. 7.

    Lu, Q. et al. A selective and efficient electrocatalyst for carbon dioxide reduction. Nat. Commun. 5, 3242 (2014).

    PubMed  Google Scholar 

  8. 8.

    Mistry, H., Varela, A. S., Kühl, S., Strasser, P. & Cuenya, B. R. Nanostructured electrocatalysts with tunable activity and selectivity. Nat. Rev. Mater. 1, 16009 (2016).

    CAS  Google Scholar 

  9. 9.

    Angamuthu, R., Byers, P., Lutz, M., Spek, A. L. & Bouwman, E. Electrocatalytic CO2 conversion to oxalate by a copper complex. Science 327, 313–315 (2010).

    CAS  PubMed  Google Scholar 

  10. 10.

    Li, Y. et al. Structure-sensitive CO2 electroreduction to hydrocarbons on ultrathin 5-fold twinned copper nanowires. Nano Lett. 17, 1312–1317 (2017).

    CAS  PubMed  Google Scholar 

  11. 11.

    Cheng, T., Xiao, H. & Goddard, W. A. III Reaction mechanisms for the electrochemical reduction of CO2 to CO and formate on the Cu(100) surface at 298 K from quantum mechanics free energy calculations with explicit water. J. Am. Chem. Soc. 138, 13802–13805 (2016).

    CAS  PubMed  Google Scholar 

  12. 12.

    Raciti, D., Mao, M., Park, J. H. & Wang, C. Local pH effect in the CO2 reduction reaction on high-surface-area copper electrocatalysts. J. Electrochem. Soc. 165, F799 (2018).

    CAS  Google Scholar 

  13. 13.

    Li, C. W. & Kanan, M. W. CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J. Am. Chem. Soc. 134, 7231–7234 (2012).

    CAS  PubMed  Google Scholar 

  14. 14.

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

    PubMed  PubMed Central  Google Scholar 

  15. 15.

    Choi, C. et al. A highly active star decahedron Cu nanocatalyst for hydrocarbon production at low overpotentials. Adv. Mater. 31, 1805405 (2019).

    Google Scholar 

  16. 16.

    Feng, X., Jiang, K., Fan, S. & Kanan, M. W. Grain-boundary-dependent CO2 electroreduction activity. J. Am. Chem. Soc. 137, 4606–4609 (2015).

    CAS  PubMed  Google Scholar 

  17. 17.

    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).

    CAS  PubMed  Google Scholar 

  18. 18.

    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).

    CAS  PubMed  Google Scholar 

  19. 19.

    Favaro, M. et al. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. Proc. Natl Acad. Sci. USA https://doi.org/10.1073/pnas.1701405114 (2017).

  20. 20.

    Lum, Y. & Ager, J. W. Stability of residual oxides in oxide‐derived copper catalysts for electrochemical CO2 reduction investigated with 18O labeling. Angew. Chem. Int. Ed. Engl. 57, 551–554 (2018).

    CAS  PubMed  Google Scholar 

  21. 21.

    Ethylene—Global Market Trajectory and Analytics https://www.researchandmarkets.com/reports/354876/ethylene_global_market_trajectory_and_analytics (Research and Markets, 2020).

  22. 22.

    Cheng, T., Xiao, H. & Goddard, W. A. Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K. Proc. Natl Acad. Sci. USA 114, 1795–1800 (2017).

    CAS  PubMed  Google Scholar 

  23. 23.

    Cheng, T., Xiao, H. & Goddard, W. A. Nature of the active sites for CO reduction on copper nanoparticles; suggestions for optimizing performance. J. Am. Chem. Soc. 139, 11642–11645 (2017).

    CAS  PubMed  Google Scholar 

  24. 24.

    Hori, Y., Takahashi, I., Koga, O. & Hoshi, N. Selective formation of C2 compounds from electrochemical reduction of CO2 at a series of copper single crystal electrodes. J. Phys. Chem. B 106, 15–17 (2002).

    CAS  Google Scholar 

  25. 25.

    Jin, M. et al. Shape‐controlled synthesis of copper nanocrystals in an aqueous solution with glucose as a reducing agent and hexadecylamine as a capping agent. Angew. Chem. Int. Ed. 50, 10560–10564 (2011).

    CAS  Google Scholar 

  26. 26.

    Yang, H. J., He, S. Y. & Tuan, H. Y. Self-seeded growth of five-fold twinned copper nanowires: mechanistic study, characterization, and SERS applications. Langmuir 30, 602–610 (2014).

    CAS  PubMed  Google Scholar 

  27. 27.

    Mandal, L. et al. Investigating the role of copper oxide in electrochemical CO2 reduction in real time. ACS Appl. Mater. Inter. 10, 8574–8584 (2018).

    CAS  Google Scholar 

  28. 28.

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

    CAS  Google Scholar 

  29. 29.

    Droog, J. M. & Schlenter, B. Oxygen electrosorption on copper single crystal electrodes in sodium hydroxide solution. J. Electroanal. Chem. 112, 387–390 (1980).

    CAS  Google Scholar 

  30. 30.

    De Chialvo, M. G., Zerbino, J. O., Marchiano, S. L. & Arvia, A. J. Correlation of electrochemical and ellipsometric data in relation to the kinetics and mechanism of Cu2O electroformation in alkaline solutions. J. Appl. Electrochem. 16, 517–526 (1986).

    Google Scholar 

  31. 31.

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

    CAS  Google Scholar 

  32. 32.

    Luc, W. et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat. Catal. 1, 423–430 (2019).

    Google Scholar 

  33. 33.

    De Chialvo, M. G., Marchiano, S. L. & Arvia, A. J. The mechanism of oxidation of copper in alkaline solutions. J. Appl. Electrochem. 14, 165–175 (1984).

    Google Scholar 

  34. 34.

    Zhang, S., Kang, P. & Meyer, T. J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J. Am. Chem. Soc. 136, 1734–1737 (2014).

    CAS  PubMed  Google Scholar 

  35. 35.

    Tian, F. H. & Wang, Z. X. Adsorption of an O atom on the Cu(311) step defective surface. J. Phys. Chem. B 108, 1392–1395 (2004).

    CAS  Google Scholar 

  36. 36.

    Hori, Y., Wakebe, H., Tsukamoto, T. & Koga, O. Adsorption of CO accompanied with simultaneous charge transfer on copper single crystal electrodes related with electrochemical reduction of CO2 to hydrocarbons. Surf. Sci. 335, 258–263 (1995).

    CAS  Google Scholar 

  37. 37.

    Baricuatro, J. H., Kim, Y. G., Korzeniewski, C. L. & Soriaga, M. P. Seriatim ECSTM–ECPMIRS of the adsorption of carbon monoxide on Cu(100) in alkaline solution at CO2-reduction potentials. Electrochem. Commun. 91, 1–4 (2018).

    CAS  Google Scholar 

  38. 38.

    Resasco, J. et al. Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. J. Am. Chem. Soc. 139, 11277–11287 (2017).

    CAS  PubMed  Google Scholar 

  39. 39.

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

    CAS  PubMed  Google Scholar 

  40. 40.

    Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 13, 4998 (2017).

    Google Scholar 

  41. 41.

    Yamamoto, S. et al. In situ X-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions. J. Phys. Condens. Matter 20, 184025 (2008).

    Google Scholar 

  42. 42.

    Xiao, H., Cheng, T. & Goddard, W. A. III Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J. Am. Chem. Soc. 139, 130–136 (2016).

    PubMed  Google Scholar 

  43. 43.

    DeWulf, D. W., Jin, T. & Bard, A. J. Electrochemical and surface studies of carbon dioxide reduction to methane and ethylene at copper electrodes in aqueous solutions. J. Electrochem. Soc. 136, 1686–1691 (1989).

    CAS  Google Scholar 

  44. 44.

    Engelbrecht, A. et al. On the electrochemical CO2 reduction at copper sheet electrodes with enhanced long-term stability by pulsed electrolysis. J. Electrochem. Soc. 165, J3059–J3068 (2018).

    CAS  Google Scholar 

  45. 45.

    Zhu, W. et al. Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. J. Am. Chem. Soc. 135, 16833–16836 (2013).

    CAS  PubMed  Google Scholar 

  46. 46.

    Kresse, G., Furthmüller, J. & Hafner, J. Theory of the crystal structures of selenium and tellurium: the effect of generalized-gradient corrections to the local-density approximation. Phys. Rev. B 50, 13181 (1994).

    CAS  Google Scholar 

  47. 47.

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    CAS  Google Scholar 

  48. 48.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

    CAS  Google Scholar 

  49. 49.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

    CAS  Google Scholar 

  50. 50.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999).

    CAS  Google Scholar 

  51. 51.

    Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).

    PubMed  Google Scholar 

  52. 52.

    Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).

    Google Scholar 

  53. 53.

    Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle point. J. Chem. Phys. 113, 9978 (2000).

    CAS  Google Scholar 

  54. 54.

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

    CAS  PubMed  Google Scholar 

  55. 55.

    Kim, D., Kley, C. S., Li, Y. & Yang, P. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2–C3 products. Proc. Natl Acad. Sci. USA 114, 10560–10565 (2017).

    CAS  PubMed  Google Scholar 

  56. 56.

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

    Google Scholar 

  57. 57.

    Kim, J. et al. Branched copper oxide nanoparticles induce highly selective ethylene production by electrochemical carbon dioxide reduction. J. Am. Chem. Soc. 141, 6986–6994 (2019).

    CAS  PubMed  Google Scholar 

  58. 58.

    Jung, H. et al. Electrochemical fragmentation of Cu2O nanoparticles enhancing selective C–C coupling from CO2 reduction reaction. J. Am. Chem. Soc. 141, 4624–4633 (2019).

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The TEM work was conducted using the facilities in the Electron Imaging Center at the California NanoSystems Institute at the University of California Los Angles and the Irvine Materials Research Institute at the University of California Irvine. C.C., J.C., X.D. and Y.H. acknowledge support from the Office of Naval Research (ONR) under grant no. N000141712608. S.K., 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. C.L., S.K. and H.M.L. used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562. C.L. and H.M.L. were also supported by a National Research Foundation (NRF) of Korea grant funded by the Korean Government (no. NRF-2017R1E1A1A03071049). The work done at the University of California Irvine was supported by the Irvine Materials Research Institute and ExxonMobil.

Author information

Affiliations

Authors

Contributions

C.C. designed and conducted most of the experiments, analysed all the data and prepared the manuscript. S.K., T.C. and W.A.G. performed the density theoretical calculations and prepared the manuscript. M.X., P.T. and X.P. took SEI and bright-field scanning transmission electron microscopy images. J.C., C.L., H.M.L and X.D. assisted in the experiments and the preparation of the manuscript. Y.H. initiated the study, oversaw the project and wrote the manuscript. All the authors discussed the results and contributed to the manuscript.

Corresponding authors

Correspondence to William A. Goddard III or Yu Huang.

Ethics declarations

Competing interests

The authors declare no competing interests.

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 Figs. 1–15, Tables 1–6 and references.

Supplementary Data 1

Atomic structures of the initial state, transition state and final state

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Choi, C., Kwon, S., Cheng, T. et al. Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4. Nat Catal 3, 804–812 (2020). https://doi.org/10.1038/s41929-020-00504-x

Download citation

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