Abstract

The renewable-energy-powered electrocatalytic conversion of carbon dioxide and carbon monoxide into carbon-based fuels provides a means for the storage of renewable energy. We sought to convert carbon monoxide—an increasingly available and low-cost feedstock that could benefit from an energy-efficient upgrade in value—into n-propanol, an alcohol that can be directly used as engine fuel. Here we report that a catalyst consisting of highly fragmented copper structures can bring C1 and C2 binding sites together, and thereby promote further coupling of these intermediates into n-propanol. Using this strategy, we achieved an n-propanol selectivity of 20% Faradaic efficiency at a low potential of −0.45 V versus the reversible hydrogen electrode (ohmic corrected) with a full-cell energetic efficiency of 10.8%. We achieved a high reaction rate that corresponds to a partial current density of 8.5 mA cm–2 for n-propanol.

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 on 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.

    Won, D. H. et al. Highly efficient, selective, and stable CO2 electroreduction on a hexagonal Zn catalyst. Angew. Chem. Int. Ed. 55, 9297–9300 (2016).

  2. 2.

    Ma, M., Trześniewski, B. J., Xie, J. & Smith, W. A. Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts. Angew. Chem. Int. Ed. 55, 9748–9752 (2016).

  3. 3.

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

  4. 4.

    Verma, S. et al. Insights into the low overpotential electroreduction of CO2 to CO on a supported gold catalyst in an alkaline flow electrolyzer. ACS Energy Lett. 3, 193–198 (2017).

  5. 5.

    Dai, L. et al. Ultrastable atomic copper nanosheets for selective electrochemical reduction of carbon dioxide. Sci. Adv. 3, e1701069 (2017).

  6. 6.

    Gao, S. et al. Ultrathin Co3O4 layers realizing optimized CO2 electroreduction to formate. Angew. Chem. Int. Ed. 55, 698–702 (2016).

  7. 7.

    Wang, Y., Zhou, J., Lv, W., Fang, H. & Wang, W. Electrochemical reduction of CO2 to formate catalyzed by electroplated tin coating on copper foam. Appl. Surf. Sci. 362, 394–398 (2016).

  8. 8.

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

  9. 9.

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

  10. 10.

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

  11. 11.

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

  12. 12.

    Pang, Y. et al. Joint tuning of nanostructured Cu-oxide morphology and local electrolyte programs high-rate CO2 reduction to C2H4. Green Chem. 19, 4023–4030 (2017).

  13. 13.

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

  14. 14.

    Ma, S. et al. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu–Pd catalysts with different mixing patterns. J. Am. Chem. Soc. 139, 47–50 (2016).

  15. 15.

    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).

  16. 16.

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

  17. 17.

    Papa, A. J. in Ullmann’s Encyclopedia of Industrial Chemistry (eds Elvers, B. et al.) 243–254 (Wiley, Weinheim, 2000).

  18. 18.

    Hori, Y., Murata, A., Takahashi, R. & Suzuki, S. Enhanced formation of ethylene and alcohols at ambient temperature and pressure in electrochemical reduction of carbon dioxide at a copper electrode. J. Chem. Soc. Chem. Comm. 1, 17–19 (1988).

  19. 19.

    Ren, D., Wong, N. T., Handoko, A. D., Huang, Y. & Yeo, B. S. Mechanistic insights into the enhanced activity and stability of agglomerated Cu nanocrystals for the electrochemical reduction of carbon dioxide to n-propanol. J. Phys. Chem. Lett. 7, 20–24 (2015).

  20. 20.

    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).

  21. 21.

    Rahaman, M., Dutta, A., Zanetti, A. & Broekmann, P. Electrochemical reduction of CO2 into multicarbon alcohols on activated Cu mesh catalysts: an identical location (IL) study. ACS Catal. 7, 7946–7956 (2017).

  22. 22.

    Jiang, K. et al. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 1, 111–119 (2018).

  23. 23.

    Zhuang, T. T. et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421–428 (2018).

  24. 24.

    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. Phys. Chem. Lett. 6, 4073–4082 (2015).

  25. 25.

    Ou, L., Long, W., Chen, Y. & Jin, J. New reduction mechanism of CO dimer by hydrogenation to C2H4 on a Cu(100) surface: theoretical insight into the kinetics of the elementary steps. RSC Adv. 5, 96281–96289 (2015).

  26. 26.

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

  27. 27.

    Birat, J. P. & Maizières-lès-Metz, D. Global Technology Roadmap for CCS in Industry—Steel Sectorial Report (UNIDO Global Technology Roadmap for CCS in Industry—Sectoral Experts Meeting, Amsterdam, 2010.)

  28. 28.

    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).

  29. 29.

    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).

  30. 30.

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

  31. 31.

    Bertheussen, E. et al. Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper. Angew. Chem. Int. Ed. 55, 1450–1454 (2016).

  32. 32.

    Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).

  33. 33.

    Zhuang, T. T. et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat. Cat. 1, 946–951 (2018).

  34. 34.

    Li, J. et al. Copper adparticle enabled selective electrosynthesis of n-propanol. Nat. Commun. 9, 4614 (2018).

  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.

    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).

  37. 37.

    Xiao, H., Cheng, T. & Goddard, W. A. Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J. Am. Chem. Soc. 139, 130–136 (2017).

  38. 38.

    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).

  39. 39.

    Zhuang, T. T. et al. Controlled synthesis of kinked ultrathin ZnS nanorods/nanowires triggered by chloride ions: a case study. Small 10, 1394–1402 (2014).

  40. 40.

    Lee, S., Kim, D. & Lee, J. Electrocatalytic production of C3–C4 compounds by conversion of CO2 on a chloride-induced bi-phasic Cu2O–Cu catalyst. Angew. Chem. Int. Ed. 54, 14701–14705 (2015).

  41. 41.

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

  42. 42.

    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).

  43. 43.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  44. 44.

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

  45. 45.

    Kresse, G. & Hafner, J. Ab-Initio molecular-dynamics simulation of the liquid–metal amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

  46. 46.

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

  47. 47.

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

  48. 48.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

  49. 49.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

  50. 50.

    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).

  51. 51.

    Michaelides, A. et al. Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces. J. Am. Chem. Soc. 125, 3704–3705 (2003).

  52. 52.

    Liu, Z. P. & Hu, P. General rules for predicting where a catalytic reaction should occur on metal surfaces: a density functional theory study of C–H and C–O bond breaking/making on flat, stepped, and kinked metal surfaces. J. Am. Chem. Soc. 125, 1958–1967 (2003).

  53. 53.

    Alavi, A., Hu, P. J., Deutsch, T., Silvestrelli, P. L. & Hutter, J. CO oxidation on Pt(111): an ab initio density functional theory study. Phys. Rev. Lett. 80, 3650–3653 (1998).

  54. 54.

    Rumble, J. R. CRC Handbook of Chemistry and Physics 99th edn, Section 5 (CRC Press, 2018).

  55. 55.

    Speight, J. G. Lange’s Handbook of Chemistry 16th edn, Section 6 (McGraw-Hill Companies New York, 2005).

  56. 56.

    Zheng, X. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption. Nat. Chem. 10, 149 (2018).

  57. 57.

    Zhou, H. et al. Water splitting by electrolysis at high current density under 1.6 volt. Energy Environ. Sci. 11, 2858–2864 (2018).

Download references

Acknowledgements

This work was supported by the Ontario Research Fund Research-Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the CIFAR Bio-Inspired Solar Energy programme, and the University of Toronto Connaught Program. This research used synchrotron resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by the Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The authors thank Z. Finfrock and M. J. Ward for technical support at the Sector 20BM beamline. D.S. acknowledges the NSERC E.W.R. Steacie Memorial Fellowship. J.L. acknowledges the Banting Postdoctoral Fellowships program. 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.

Author information

Author notes

  1. These authors contributed equally: Yuanjie Pang and Jun Li.

Affiliations

  1. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, ON, Canada

    • Yuanjie Pang
    • , Jun Li
    • , Jonathan P. Edwards
    • , Yi Xu
    •  & David Sinton
  2. Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON, Canada

    • Yuanjie Pang
    • , Jun Li
    • , Ziyun Wang
    • , Chih-Shan Tan
    • , Tao-Tao Zhuang
    • , Zhi-Qin Liang
    • , Chengqin Zou
    • , Xue Wang
    • , Fengwang Li
    • , Cao-Thang Dinh
    • , Miao Zhong
    •  & Edward H. Sargent
  3. School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, Hubei, China

    • Yuanjie Pang
    • , Yuanhao Lou
    •  & Dan Wu
  4. Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Hsinchu, Taiwan

    • Pei-Lun Hsieh
    •  & Lih-Juann Chen
  5. Department of Materials Science and Engineering, University of Toronto, Toronto, ON, Canada

    • Phil De Luna

Authors

  1. Search for Yuanjie Pang in:

  2. Search for Jun Li in:

  3. Search for Ziyun Wang in:

  4. Search for Chih-Shan Tan in:

  5. Search for Pei-Lun Hsieh in:

  6. Search for Tao-Tao Zhuang in:

  7. Search for Zhi-Qin Liang in:

  8. Search for Chengqin Zou in:

  9. Search for Xue Wang in:

  10. Search for Phil De Luna in:

  11. Search for Jonathan P. Edwards in:

  12. Search for Yi Xu in:

  13. Search for Fengwang Li in:

  14. Search for Cao-Thang Dinh in:

  15. Search for Miao Zhong in:

  16. Search for Yuanhao Lou in:

  17. Search for Dan Wu in:

  18. Search for Lih-Juann Chen in:

  19. Search for Edward H. Sargent in:

  20. Search for David Sinton in:

Contributions

E.H.S. and D.S. supervised the project. Y.P. and J.L. designed the CORR experiments. Y.P., J.L., T.-T.Z., X.W. and Y.X. carried out the CORR experiments. P.D.L. assisted the catalyst preparation. J.L. carried out the operando XAS characterization. Z.W. performed the DFT calculations. C.-S.T., P.-L.H. and L.-J.C. carried out TEM imaging. Y.P., Y. L. and D.W. performed the TEM analysis. Y.P., J.L., Z.-Q.L, C.Z., J.P.E., C.-T.D., F.L. and M.Z. carried out the product detection via NMR and gas chromatography. Z.-Q.L. carried out the XRD characterization. All the authors discussed the results and assisted during manuscript preparation.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Edward H. Sargent or David Sinton.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–42 and Supplementary Tables 1–2.

  2. Supplementary Data 1

    Data associated to Fig. 4.

  3. Supplementary Data 2

    Optimized geometry for the initial state of CO dimerization on copper interface model.

  4. Supplementary Data 3

    Optimized geometry for the final state of CO dimerization on copper interface model.

  5. Supplementary Data 4

    Optimized geometry for the transition state of CO dimerization on copper interface model.

  6. Supplementary Data 5

    Optimized geometry for the initial state of CO-OCCO coupling on copper interface model.

  7. Supplementary Data 6

    Optimized geometry for the final state of of CO-OCCO coupling on copper interface model.

  8. Supplementary Data 7

    Optimized geometry for the transition state of CO-OCCO coupling on copper interface model.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41929-019-0225-7