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Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper


Direct electrochemical conversion of CO2 to ethanol offers a promising strategy to lower CO2 emissions while storing energy from renewable electricity. However, current electrocatalysts offer only limited selectivity toward ethanol. Here we report a carbon-supported copper (Cu) catalyst, synthesized by an amalgamated Cu–Li method, that achieves a single-product Faradaic efficiency (FE) of 91% at −0.7 V (versus the reversible hydrogen electrode) and onset potential as low as −0.4 V (reversible hydrogen electrode) for electrocatalytic CO2-to-ethanol conversion. The catalyst operated stably over 16 h. The FE of ethanol was highly sensitive to the initial dispersion of Cu atoms and decreased significantly when CuO and large Cu clusters become predominant species. Operando X-ray absorption spectroscopy identified a reversible transformation from atomically dispersed Cu atoms to Cun clusters (n = 3 and 4) on application of electrochemical conditions. First-principles calculations further elucidate the possible catalytic mechanism of CO2 reduction over Cun.

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Fig. 1: Catalyst synthesis.
Fig. 2: Catalyst structure characterizations.
Fig. 3: Electrocatalytic CO2RR measurement over Cu/C-0.4.
Fig. 4: Electrochemical properties of Cu/C at different loading.
Fig. 5 : Operando XAS study on the Cu CO2RR active site.
Fig. 6: DFT calculations.

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Data availability

The authors declare that all data are available in the main text, Supplementary Information and Source Data files. Data generated from DFT calculations can be found in Supplementary Data 1 and Supplementary Data 2. Source data are provided with this paper.


  1. Goeppert, A., Czaun, M., Jones, J.-P., Surya Prakash, G. K. & Olah, G. A. CO2 capture and recycling to chemicals, fuels and materials: enabling technologies. Chem. Soc. Rev. 43, 7995–8048 (2014).

    Article  Google Scholar 

  2. Zhou, Y. S. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat. Chem. 10, 974–980 (2018).

    Article  Google Scholar 

  3. Tilman, D., Hill, J. & Lehman, C. Carbon-negative biofuels from low-input high diversity grassland biomass. Science 314, 1598–1600 (2006).

    Article  Google Scholar 

  4. Lehmann, J. A handful of carbon. Nature 447, 143–144 (2007).

    Article  Google Scholar 

  5. Zheng, X. L. et al. Sulfur-modulated tin sites enable highly selective electrochemical reduction of CO2 to formate. Joule 1, 794–805 (2017).

    Article  Google Scholar 

  6. Fang, Y. & Flake, J. Electrochemical reduction of CO2 at functionalized Au electrodes. J. Am. Chem. Soc. 139, 3399–3405 (2017).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  9. Kim, D., Resasco, J., Yu, Y., Asiri, A. & Yang, P. D. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat. Commun. 5, 4948 (2016).

    Article  Google Scholar 

  10. Zheng, X. et al. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. Nat. Catal. 1, 1–7 (2018).

    Article  Google Scholar 

  11. 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).

    Article  Google Scholar 

  12. Chen, Y. H. & Kanan, M. W. Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. J. Am. Chem. Soc. 134, 1986–1989 (2015).

    Article  Google Scholar 

  13. Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).

    Article  Google Scholar 

  14. Crawley, M. R. et al. Rhenium phosphazane complexes for electrocatalytic CO2 reduction. Organometallics 38, 1664–1676 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Google Scholar 

  17. Xie, H., Wang, T. Y., Liang, J. S., Li, Q. & Sun, S. H. Cu-based nanocatalysts for electrochemical reduction of CO2. Nano Today 21, 41–54 (2018).

    Article  Google Scholar 

  18. 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 (2017).

    Article  Google Scholar 

  19. Duan, Y. X. et al. Amorphizing of Cu nanoparticles toward highly efficient and robust electrocatalyst for CO2 reduction to liquid fuels with high Faradaic efficiencies. Adv. Mater. 30, 1706194 (2018).

    Article  Google Scholar 

  20. Weng, Z. et al. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 9, 415 (2018).

    Article  Google Scholar 

  21. Yang, H. B. et al. Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction. Nat. Energy 3, 140–147 (2018).

    Article  Google Scholar 

  22. Dilan Karapinar et al. Electroreduction of CO2 on single-site copper-nitrogen-doped carbon material: selective formation of ethanol and reversible restructuration of the metal sites. Angew. Chem. Int. Ed. 58, 2–8 (2019).

    Article  Google Scholar 

  23. Wei, H. S. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2017).

    Article  Google Scholar 

  24. House, J. E. Inorganic Chemistry (Elsevier Inc., 2013).

  25. Jiang, K. et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction. Energy Environ. Sci. 11, 893–903 (2018).

    Article  Google Scholar 

  26. Malta, G. et al. Identification of single-site gold catalysis in acetylene hydrochlorination. Science 355, 1399–1403 (2017).

    Article  Google Scholar 

  27. Wu, J. Achieving highly efficient, selective, and stable CO2 reduction on nitrogen-doped carbon nanotubes. ACS Nano. 9, 5364–5371 (2015).

    Article  Google Scholar 

  28. Xie, M. S. et al. Amino acid modified copper electrodes for the enhanced selective electroreduction of carbon dioxide towards hydrocarbons. Energy Environ. Sci. 9, 1687–1695 (2016).

    Article  Google Scholar 

  29. Guvelioglu, G. H., Ma, P. P. & He, X. Y. First principles studies on the growth of small Cu clusters and the dissociative chemisorption of H2. Phys. Rev. B. 73, 155436–155446 (2006).

    Article  Google Scholar 

  30. Peterson, A. A., Abild-Pedersen, F., Studt, Felix, Rossmeisl, J. & Jens Nørskov, K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010).

    Article  Google Scholar 

  31. Xu, T. et al. Synthesis of supported platinum nanoparticles from Li-Pt solid solution. J. Am. Chem. Soc. 132, 2151–2153 (2010).

    Article  Google Scholar 

  32. Datta, S. et al. Use of X-Ray absorption spectroscopy (XAS) to speciate manganese in airborne particulate matter from 5 counties across the US. Environ. Sci. Technol. 46, 3101–3109 (2012).

    Article  Google Scholar 

  33. Li, S. J., Han, K. H., Si, P. C., Li, J. X. & Lu, C. M. High–performance activated carbons prepared by KOH activation of gulfweed for supercapacitors. Int. J. Electrochem. Sci. 13, 1728–1743 (2018).

    Article  Google Scholar 

  34. 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).

    Article  Google Scholar 

  35. 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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  37. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  38. Kresse, G. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  39. Kresse, G. Theory of the crystal structures of selenium and tellurium: the effect of generalized-gradient corrections to the local-density approximation. Phys. Rev. B 49, 14251–14269 (1994).

    Article  Google Scholar 

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

    Article  Google Scholar 

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This material is based on work supported by Laboratory Directed Research and Development funding from Argonne National Laboratory, provided by the Director, Office of Science, of the US Department of Energy (DOE) under contract no. DE-AC02-06CH11357. The works performed at Argonne National Laboratory’s Center for Nanoscale Materials and APS, US DOE Office of Science User Facilities, are supported by Office of Science, US DOE under contract no. DE-AC02-06CH11357. Part of the DFT calculations were also performed using the computational resources provided by the Laboratory Computing Resource Center at the Argonne National Laboratory. T.X. acknowledges the financial support from the XSD visiting scientist program at APS at Argonne. C.L.’s work is supported by the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under contract no. DE-AC02-06CH11357 (Argonne National Laboratory). The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof; neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, nor usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. We also acknowledge I. Hwang for verification of our EXAFS simulation by Artemis.

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Authors and Affiliations



D.-J.L. and T.X. designed and supervised the experiment with assistance from C.L. and T.L. C.L. led and H.H. assisted the computational investigations. T.L. led and H.X., L.C., Y.L., C.S., J.V.M. and R.E.W. assisted the characterization of catalysts structure and catalysis products. H.X. and D.R. synthesized catalysts, conducted electrochemical study and data analysis. H.X., H.H., C.L., D.-J.L. and T.X. wrote the manuscript.

Corresponding authors

Correspondence to Cong Liu, Tao Li, Di-Jia Liu or Tao Xu.

Ethics declarations

Competing interests

An US patent application (US 2019/0276943 A1) on amalgamated metal—Li catalyst synthesis for CO2 conversion with D.-J. Liu, T. Xu, H. Xu and D. Rebollar as the coinventors was filed by UCHICAGO ARGONNE, LLC. The authors declare no other competing interests.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–26, Tables 1–14 and refs. 1–34.

Supplementary Data 1

Cif files from DFT study for Cu3 clusters.

Supplementary Data 2

Cif files for CO reaction pathway.

Supplementary Data 3

Source data of Supplementary Fig. 19 for the error bar calculation.

Source data

Source Data Fig. 3

Source data of Fig. 3b for the ethanol error bar calculation and total error bar calculation.

Source Data Fig. 4

Source data of Fig. 4a,b for the error bar calculation.

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Xu, H., Rebollar, D., He, H. et al. Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper. Nat Energy 5, 623–632 (2020).

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