Article | Published:

Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction

Nature Catalysisvolume 2pages8693 (2019) | Download Citation

Abstract

Carbon dioxide electroreduction in aqueous media using Cu catalysts can generate many different C2 and C3 products, which leads to the question whether all products are generated from the same types of active sites or if product-specific active sites are responsible for certain products. Here, by reducing mixtures of 13CO and 12CO2, we show that oxide-derived Cu catalysts have three different types of active sites for C–C coupled products, one that produces ethanol and acetate, another that produces ethylene and yet another that produces 1-propanol. In contrast, we do not find evidence of product-specific sites on polycrystalline Cu and oriented (100) and (111) Cu surfaces. Analysis of the isotopic composition of the products leads to the prediction that the adsorption energy of *COOH (the product of the first step of CO2 reduction) may be a descriptor for the product selectivity of a given active site. These new insights should enable highly selective catalysts to be developed.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Data availability

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

Additional information

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

References

  1. 1.

    IPCC Climate Change 2014: Synthesis Report (eds Core Writing Team, Pachauri, R. K. & Meyer L. A.) (IPCC, 2014).

  2. 2.

    Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).

  3. 3.

    Hori, Y. Electrochemical CO2 Reduction on Metal Electrodes. in Modern Aspects of Electrochemistry No. 42 (eds Vayenas, C., White, R. & Gamboa-Aldeco, M.) 89–189 (Springer, New York, 2008).

  4. 4.

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

  5. 5.

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

  6. 6.

    Hori, Y., Murata, A. & Takahashi, R. Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution. J. Chem. Soc. Faraday Trans. 1 85, 2309 (1989).

  7. 7.

    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).

  8. 8.

    Kuhl, K. P. et al. Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J. Am. Chem. Soc. 136, 14107–14113 (2014).

  9. 9.

    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).

  10. 10.

    Peterson, A. A. et al. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010).

  11. 11.

    Cheng, T., Xiao, H. & Goddard, W. A. 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).

  12. 12.

    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).

  13. 13.

    Hori, Y., Takahashi, R., Yoshinami, Y. & Murata, A. Electrochemical reduction of CO at a copper electrode. J. Phys. Chem. B 101, 7075–7081 (1997).

  14. 14.

    Schouten, K. J. P., Qin, Z., Gallent, E. P. & Koper, M. T. M. Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. J. Am. Chem. Soc. 134, 9864–9867 (2012).

  15. 15.

    Kortlever, R., Shen, J., Schouten, K. J. P., Calle-Vallejo, F. & Koper, M. T. M. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide. J. Phys. Chem. Lett. 6, 4073–4082 (2015).

  16. 16.

    Calle-Vallejo, F. & Koper, M. T. M. Theoretical considerations on the electroreduction of CO to C2 species on Cu(100) electrodes. Angew. Chem. 125, 7423–7426 (2013).

  17. 17.

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

  18. 18.

    Ma, S. et al. One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer. J. Power Sources 301, 219–228 (2016).

  19. 19.

    Peterson, A. A. & Nørskov, J. K. Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts. J. Phys. Chem. Lett. 3, 251–258 (2012).

  20. 20.

    Hansen, H. A., Varley, J. B., Peterson, A. A. & Nørskov, J. K. Understanding trends in the electrocatalytic activity of metals and enzymes for CO2 reduction to CO. J. Phys. Chem. Lett. 4, 388–392 (2013).

  21. 21.

    Liu, X. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 14580 (2017).

  22. 22.

    Sandberg, R. B., Montoya, J. H., Chan, K. & Nørskov, J. K. CO–CO coupling on Cu facets: coverage, strain and field effects. Surf. Sci. 654, 56–62 (2016).

  23. 23.

    Goodpaster, J. D., Bell, A. T. & Head-Gordon, M. Identification of possible pathways for C–C bond formation during electrochemical reduction of CO2: new theoretical insights from an improved electrochemical model. J. Phys. Chem. Lett. 7, 1471–1477 (2016).

  24. 24.

    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).

  25. 25.

    Ma, M., Djanashvili, K. & Smith, W. A. Controllable hydrocarbon formation from the electrochemical reduction of CO2 over Cu nanowire arrays. Angew. Chem. Int. Ed. 55, 6680–6684 (2016).

  26. 26.

    Lum, Y., Yue, B., Lobaccaro, P., Bell, A. T. & Ager, J. W. Optimizing C–C coupling on oxide-derived copper catalysts for electrochemical CO2 reduction. J. Phys. Chem. C 121, 14191–14203 (2017).

  27. 27.

    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).

  28. 28.

    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).

  29. 29.

    Kas, R., Kortlever, R., Yılmaz, H., Koper, M. T. M. & Mul, G. Manipulating the hydrocarbon selectivity of copper nanoparticles in CO2 electroreduction by process conditions. ChemElectroChem 2, 354–358 (2014).

  30. 30.

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

  31. 31.

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

  32. 32.

    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).

  33. 33.

    Roberts, F. S., Kuhl, K. P. & Nilsson, A. High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. Angew. Chem. 127, 5268–5271 (2015).

  34. 34.

    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).

  35. 35.

    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).

  36. 36.

    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).

  37. 37.

    Singh, M. R., Clark, E. L. & Bell, A. T. Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide. Phys. Chem. Chem. Phys. 17, 18924–18936 (2015).

  38. 38.

    Xiao, H., Cheng, T., Goddard, W. A. & 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).

  39. 39.

    Resasco, J., Lum, Y., Clark, E., Zeledon, J. Z. & Bell, A. T. Effects of anion identity and concentration on electrochemical reduction of CO2. ChemElectroChem 5, 1064–1072 (2018).

  40. 40.

    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).

  41. 41.

    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).

  42. 42.

    Wang, Y. et al. CO2 reduction to acetate in mixtures of ultrasmall (Cu)n,(Ag)m bimetallic nanoparticles. Proc. Natl Acad. Sci. USA 115, 278–283 (2018).

  43. 43.

    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).

  44. 44.

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

  45. 45.

    Calle-Vallejo, F. & Koper, M. T. M. Theoretical considerations on the electroreduction of CO to C2 species on Cu(100) electrodes. Angew. Chem. Int. Ed. 52, 7282–7285 (2013).

  46. 46.

    Singh, M. R., Goodpaster, J. D., Weber, A. Z., Head-Gordon, M. & Bell, A. T. Mechanistic insights into electrochemical reduction of CO2 over Ag using density functional theory and transport models. Proc. Natl Acad. Sci. USA 114, E8812–E8821 (2017).

  47. 47.

    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).

  48. 48.

    Pérez-Gallent, E., Marcandalli, G., Figueiredo, M. C., Calle-Vallejo, F. & Koper, M. T. M. Structure- and potential-dependent cation effects on CO reduction at copper single-crystal electrodes. J. Am. Chem. Soc. 139, 16412–16419 (2017).

  49. 49.

    Chen, J. G., Jones, C. W., Linic, S. & Stamenkovic, V. R. Best practices in pursuit of topics in heterogeneous electrocatalysis. ACS Catal. 7, 6392–6393 (2017).

  50. 50.

    Lobaccaro, P. et al. Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts. Phys. Chem. Chem. Phys. 18, 26777–26785 (2016).

  51. 51.

    Linstrom, P. J. and Mallard, W. G. NIST Chemistry WebBook NIST Standard Reference Database Number 69 (National Institute of Standards and Technology, Gaithersburg).

Download references

Acknowledgements

This material is based on work performed 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. Y.L. acknowledges the support of an A*STAR National Science Scholarship. We thank A. Buckley for assistance with the 13C NMR spectroscopy and W. R. Leow for assistance with the creation of the figures.

Author information

Affiliations

  1. Joint Center for Artificial Photosynthesis and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    • Yanwei Lum
    •  & Joel W. Ager
  2. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    • Yanwei Lum
    •  & Joel W. Ager

Authors

  1. Search for Yanwei Lum in:

  2. Search for Joel W. Ager in:

Contributions

Y.L. and J.W.A. conceived and designed the experiments. Y.L. conducted all the experimental work and analysed the data. Both authors discussed the results and wrote the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Joel W. Ager.

Supplementary information

  1. Supplementary Information

    Supplementary Notes 1–14, Supplementary Figures 1–44, Supplementary Tables 1–18 and Supplementary References

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41929-018-0201-7