Abstract

Engineering copper-based catalysts that favour high-value alcohols is desired in view of the energy density, ready transport and established use of these liquid fuels. In the design of catalysts, much progress has been made to target the C–C coupling step; whereas comparatively little effort has been expended to target post-C–C coupling reaction intermediates. Here we report a class of core–shell vacancy engineering catalysts that utilize sulfur atoms in the nanoparticle core and copper vacancies in the shell to achieve efficient electrochemical CO2 reduction to propanol and ethanol. These catalysts shift selectivity away from the competing ethylene reaction and towards liquid alcohols. We increase the alcohol-to-ethylene ratio more than sixfold compared with bare-copper nanoparticles, highlighting an alternative approach to electroproduce alcohols instead of alkenes. We achieve a C2+ alcohol production rate of 126 ± 5 mA cm−2 with a selectivity of 32 ± 1% Faradaic efficiency.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Additional information

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

References

  1. 1.

    Gao, S. et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 529, 68–71 (2016).

  2. 2.

    Asadi, M. et al. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science 353, 467–470 (2016).

  3. 3.

    Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).

  4. 4.

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

  5. 5.

    Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).

  6. 6.

    Rogers, C. et al. Synergistic enhancement of electrocatalytic CO2 reduction with gold nanoparticles embedded in functional graphene nanoribbon composite electrodes. J. Am. Chem. Soc. 139, 4052–4061 (2017).

  7. 7.

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

  8. 8.

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

  9. 9.

    Saberi Safaei, T. et al. High-density nanosharp microstructures enable efficient CO2 electroreduction. Nano Lett. 16, 7224–7228 (2016).

  10. 10.

    Lei, F. et al. Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction. Nat. Commun. 7, 12697 (2016).

  11. 11.

    Klinkova, A. et al. Rational design of efficient palladium catalysts for electroreduction of carbon dioxide to formate. ACS Catal. 6, 8115–8120 (2016).

  12. 12.

    ZHU, Q.-G. et al. Cu2S on Cu foam as highly efficient electrocatalyst for reduction of CO2 to formic acid. Acta Phys. Chim. Sin. 32, 261–266 (2016).

  13. 13.

    Zhu, Q. et al. Efficient reduction of CO2 into formic acid on a lead or tin electrode using an ionic liquid catholyte mixture. Angew. Chem. Int. Ed. 55, 9012–9016 (2016).

  14. 14.

    Shinagawa, T., Larrazábal, G. O., Martín, A. J., Krumeich, F. & Perez-Ramirez, J. Sulfur-modified copper catalysts for the electrochemical reduction of carbon dioxide to formate. ACS Catal. 8, 837–844 (2017).

  15. 15.

    Huang, Y., Deng, Y., Handoko, A. D., Goh, G. K. & Yeo, B. S. Rational design of sulfur‐doped copper catalysts for the selective electroreduction of carbon dioxide to formate. ChemSusChem 11, 320–326 (2018).

  16. 16.

    Schouten, K. J. P., Calle‐Vallejo, F. & Koper, M. A step closer to the electrochemical production of liquid fuels. Angew. Chem. Int. Ed. 53, 10858–10860 (2014).

  17. 17.

    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).

  18. 18.

    Loiudice, A. et al. Tailoring copper nanocrystals towards C2 products in electrochemical CO2 reduction. Angew. Chem. Int. Ed. 55, 5789–5792 (2016).

  19. 19.

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

  20. 20.

    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).

  21. 21.

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

  22. 22.

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

  23. 23.

    Adit Maark, T. & Nanda, B. R. K. Enhancing CO2 electroreduction by tailoring strain and ligand effects in bimetallic copper–rhodium and copper–nickel heterostructures. J. Phy. Chem. C 121, 4496–4504 (2017).

  24. 24.

    van den Berg, R. et al. Structure sensitivity of Cu and CuZn catalysts relevant to industrial methanol synthesis. Nat. Commun. 7, 13057 (2016).

  25. 25.

    Xiao, H., Goddard, W. A., Cheng, T., & Liu, Y. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. Proc. Natl Acad. Sci. USA 114, 6685–6688 (2017).

  26. 26.

    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 114, 6706–6711 (2017).

  27. 27.

    Kasatkin, I., Kurr, P., Kniep, B., Trunschke, A. & Schlögl, R. Role of lattice strain and defects in copper particles on the activity of Cu/ZnO/Al2O3 catalysts for methanol synthesis. Angew. Chem. Int. Ed. 46, 7324–7327 (2007).

  28. 28.

    Liu, X. et al. Size‐controlled synthesis of Cu2‐xE (E = S, Se) nanocrystals with strong tunable near‐infrared localized surface plasmon resonance and high conductivity in thin films. Adv. Funct. Mater. 23, 1256–1264 (2013).

  29. 29.

    Luther, J. M., Jain, P. K., Ewers, T. & Alivisatos, A. P. Localized surface plasmon resonances arising from free carriers in doped quantum dots. Nat. Mater. 10, 361–366 (2011).

  30. 30.

    Hu, X. & Hirschmugl, C. Long-range metal-mediated interactions between S and CO on Cu(100). Phys. Rev. B 72, 205439 (2005).

  31. 31.

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

  32. 32.

    Montoya, J. H., Peterson, A. A. & Nørskov, J. K. Insights into C–C coupling in CO2 electroreduction on copper electrodes. ChemCatChem 5, 737–742 (2013).

  33. 33.

    Schouten, K. J. P., Kwon, Y., van der Ham, C. J. M., Qin, Z. & Koper, M. T. M. A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes. Chem. Sci. 2, 1902–1909 (2011).

  34. 34.

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

  35. 35.

    Zhuang, T. T., Fan, F. J., Gong, M. & Yu, S. H. Cu1.94S nanocrystal seed mediated solution-phase growth of unique Cu2S-PbS heteronanostructures. Chem. Commun. 48, 9762–9764 (2012).

  36. 36.

    Han, S. K., Gong, M., Yao, H. B., Wang, Z. M. & Yu, S. H. One‐pot controlled synthesis of hexagonal‐prismatic Cu1.94S‐ZnS, Cu1.94S‐ZnS‐Cu1.94S, and Cu1.94S‐ZnS‐Cu1.94S‐ZnS‐Cu1.94S heteronanostructures. Angew. Chem. Int. Ed. 51, 6365–6368 (2012).

  37. 37.

    Zhuang, T.-T. et al. Integration of semiconducting sulfides for full-spectrum solar energy absorption and efficient charge separation. Angew. Chem. Int. Ed. 55, 6396–6400 (2016).

  38. 38.

    Xie, Y. et al. Copper sulfide nanocrystals with tunable composition by reduction of covellite nanocrystals with Cu+ ions. J. Am. Chem. Soc. 135, 17630–17637 (2013).

  39. 39.

    Kvashnina, K. et al. Electronic structure of complex copper systems probed by resonant inelastic X-ray scattering at Cu L3 edge. Phys. B 404, 3559–3566 (2009).

  40. 40.

    Todd, E., Sherman, D. & Purton, J. Surface oxidation of chalcopyrite (CuFeS2) under ambient atmospheric and aqueous (pH 2–10) conditions: Cu, Fe L-and O K-edge X-ray spectroscopy. Geochim. Cosmochim. Acta 67, 2137–2146 (2003).

  41. 41.

    Chakraverty, S., Mitra, S., Mandal, K., Nambissan, P. & Chattopadhyay, S. Positron annihilation studies of some anomalous features of Ni Fe2O4 nanocrystals grown in SiO2. Phys. Rev. B 71, 024115 (2005).

  42. 42.

    Li, Z. et al. Dual vacancies: an effective strategy realizing synergistic optimization of thermoelectric property in BiCuSeO. J. Am. Chem. Soc. 137, 6587–6593 (2015).

  43. 43.

    Gao, S. et al. Highly efficient and exceptionally durable CO2 photoreduction to methanol over freestanding defective single-unit-cell bismuth vanadate layers. J. Am. Chem. Soc. 139, 3438–3445 (2017).

  44. 44.

    Ma, S., Luo, R., Moniri, S., Lan, Y. & Kenis, P. J. A. Efficient electrochemical flow system with improved anode for the conversion of CO2 to CO. J. Electrochem. Soc. 161, F1124–F1131 (2014).

  45. 45.

    Ma, S., Lan, Y., Perez, G. M. J., Moniri, S. & Kenis, P. J. A. Silver supported on titania as an active catalyst for electrochemical carbon dioxide reduction. ChemSusChem 7, 866–874 (2014).

  46. 46.

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

  47. 47.

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

  48. 48.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).

  49. 49.

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

  50. 50.

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

  51. 51.

    Muttaqien, F. et al. CO2 adsorption on the copper surfaces: van der Waals density functional and TPD studies. J. Phys. Chem. C 147, 094702 (2017).

  52. 52.

    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).

  53. 53.

    Wu, Y., Wadia, C., Ma, W., Sadtler, B. & Alivisatos, A. P. Synthesis and photovoltaic application of copper (I) sulfide nanocrystals. Nano Lett. 8, 2551–2555 (2008).

  54. 54.

    Guo, H. et al. Shape-selective formation of monodisperse copper nanospheres and nanocubes via disproportionation reaction route and their optical properties. J. Phys. Chem. C 118, 9801–9808 (2014).

Download references

Acknowledgements

This work was supported by TOTAL American Services, the Ontario Research Fund Research Excellence programme, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the CIFAR Bio-Inspired Solar Energy programme and a University of Toronto Connaught grant. S.-H.Y. acknowledges funding from the National Natural Science Foundation of China (grant 21431006) and the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (grant 21521001). All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. Z.L. acknowledges a scholarship from the China Scholarship Council (CSC) (201607090041). A.S. acknowledges Fonds de Recherche du Quebec—Nature et Technologies (FRQNT) for support in the form of a postdoctoral fellowship award. P.D.L. acknowledges NSERC for support in the form of a Canada Graduate Scholarship doctoral award. P.D.L. also wishes to acknowledge Y. Hu and the Canadian Light Source for assistance with X-ray absorption experiments. The authors thank A. Ip, Y. Wang, J. Fan, J. Li, C. Zou and Y. Zhou from the University of Toronto for fruitful discussions.

Author information

Author notes

  1. These authors contributed equally: Tao-Tao Zhuang, Zhi-Qin Liang, Ali Seifitokaldani.

Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    • Tao-Tao Zhuang
    • , Zhi-Qin Liang
    • , Ali Seifitokaldani
    • , Fanglin Che
    • , Yimeng Min
    • , Rafael Quintero-Bermudez
    • , Cao Thang Dinh
    • , Miao Zhong
    • , Bo Zhang
    • , Pei-Ning Chen
    • , Xue-Li Zheng
    • , Hongyan Liang
    •  & Edward H. Sargent
  2. Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, Collaborative Innovation Center of Suzhou Nano Science and Technology, CAS Center for Excellence in Nanoscience, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, China

    • Tao-Tao Zhuang
    • , Yi Li
    •  & Shu-Hong Yu
  3. Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

    • Phil De Luna
  4. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    • Thomas Burdyny
    • , Yuanjie Pang
    • , Jun Li
    •  & David Sinton
  5. State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei, Anhui, China

    • Fei Meng
    • , Wen-Na Ge
    •  & Bang-Jiao Ye
  6. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China

    • Bo Zhang

Authors

  1. Search for Tao-Tao Zhuang in:

  2. Search for Zhi-Qin Liang in:

  3. Search for Ali Seifitokaldani in:

  4. Search for Yi Li in:

  5. Search for Phil De Luna in:

  6. Search for Thomas Burdyny in:

  7. Search for Fanglin Che in:

  8. Search for Fei Meng in:

  9. Search for Yimeng Min in:

  10. Search for Rafael Quintero-Bermudez in:

  11. Search for Cao Thang Dinh in:

  12. Search for Yuanjie Pang in:

  13. Search for Miao Zhong in:

  14. Search for Bo Zhang in:

  15. Search for Jun Li in:

  16. Search for Pei-Ning Chen in:

  17. Search for Xue-Li Zheng in:

  18. Search for Hongyan Liang in:

  19. Search for Wen-Na Ge in:

  20. Search for Bang-Jiao Ye in:

  21. Search for David Sinton in:

  22. Search for Shu-Hong Yu in:

  23. Search for Edward H. Sargent in:

Contributions

E.H.S. and S.-H.Y. supervised the project. T.-T.Z. designed and carried out the experiments. Z.-Q.L. helped to investigate the performance measurements. A.S., F.C. and Y.M. carried out simulations. Y.L. helped to characterize the structure of catalyst. P.D.L. and R.Q.-B. performed the X-ray spectroscopy measurements. F.M. and B.-J.Y. carried out positron annihilation. All authors discussed the results and assisted during manuscript preparation.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Shu-Hong Yu or Edward H. Sargent.

Supplementary information

  1. Supplementary Information

    Supplementary Methods; Supplementary Figures 1–20; Supplementary Tables 1–11; Supplementary References

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41929-018-0084-7

Further reading