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.

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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.

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Author notes

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


  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


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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.

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

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