The electrosynthesis of higher-order alcohols from carbon dioxide and carbon monoxide addresses the need for the long-term storage of renewable electricity; unfortunately, the present-day performance remains below what is needed for practical applications. Here we report a catalyst design strategy that promotes C3 formation via the nanoconfinement of C2 intermediates, and thereby promotes C2:C1 coupling inside a reactive nanocavity. We first employed finite-element method simulations to assess the potential for the retention and binding of C2 intermediates as a function of cavity structure. We then developed a method of synthesizing open Cu nanocavity structures with a tunable geometry via the electroreduction of Cu2O cavities formed through acidic etching. The nanocavities showed a morphology-driven shift in selectivity from C2 to C3 products during the carbon monoxide electroreduction, to reach a propanol Faradaic efficiency of 21 ± 1% at a conversion rate of 7.8 ± 0.5 mA cm−2 at −0.56 V versus a reversible hydrogen electrode.

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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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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 program and University of Toronto Connaught grant. The authors thank T. P. Wu, Z. Finfrock and L. Ma for technical support at the 9BM beam-line of the Advanced Photon Source (Lemont, IL). This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by 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. 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). The authors thank X. Wang and A. Seifitokaldani from the University of Toronto for fruitful discussions.

Author information

Author notes

  1. These authors contributed equally: Tao-Tao Zhuang and Yuanjie Pang.


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

    • Tao-Tao Zhuang
    • , Yuanjie Pang
    • , Zhi-Qin Liang
    • , Ziyun Wang
    • , Chih-Shan Tan
    • , Jun Li
    • , Cao Thang Dinh
    • , Hui-Hui Li
    • , Mengxia Liu
    • , Yuhang Wang
    • , Fengwang Li
    • , Andrew Proppe
    • , Andrew Johnston
    • , Dae-Hyun Nam
    • , Alexander H. Ip
    • , Hairen Tan
    •  & Edward H. Sargent
  2. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    • Yuanjie Pang
    • , Jun Li
    • , Thomas Burdyny
    •  & David Sinton
  3. School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, Hubei, China

    • Yuanjie Pang
  4. 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

    • Yi Li
    • , Hui-Hui Li
    • , Zhen-Yu Wu
    • , Ya-Rong Zheng
    •  & Shu-Hong Yu
  5. Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

    • Phil De Luna
  6. Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan

    • Pei-Lun Hsieh
    •  & Lih-Juann Chen
  7. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

    • Andrew Proppe
    •  & Shana O. Kelley
  8. Department of Pharmaceutical Sciences, Leslie Dan Faculty of Pharmacy, University of Toronto, Toronto, Ontario, Canada

    • Shana O. Kelley


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E.H.S. and D.S. supervised the project. T.-T.Z. designed the structures, carried out the experiments and wrote the paper. Y.P. carried out the FEM simulations. Z.Q.L. and Y.L. helped to synthesize the catalysts and collect the electroreduction performance data. Z.W. helped to do the DFT simulations. C.-S.T. and P.-L.H. helped to characterize the morphology of the catalyst. J.L. performed the X-ray spectroscopy measurements. M.L., A.P. and A.J. carried out the grazing incidence wide-angle X-ray scattering measurements. All the authors discussed the results and assisted during the manuscript preparation.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to David Sinton or Edward H. Sargent.

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    Supplementary Methods, Supplementary Figures 1–18, Supplementary Tables 1–5 and Supplementary References

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