The electrochemical reduction of CO2 to multi-carbon products has attracted much attention because it provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the efficiency of CO2 conversion to C2 products remains below that necessary for its implementation at scale. Modifying the local electronic structure of copper with positive valence sites has been predicted to boost conversion to C2 products. Here, we use boron to tune the ratio of Cuδ+ to Cu0 active sites and improve both stability and C2-product generation. Simulations show that the ability to tune the average oxidation state of copper enables control over CO adsorption and dimerization, and makes it possible to implement a preference for the electrosynthesis of C2 products. We report experimentally a C2 Faradaic efficiency of 79 ± 2% on boron-doped copper catalysts and further show that boron doping leads to catalysts that are stable for in excess of ~40 hours while electrochemically reducing CO2 to multi-carbon hydrocarbons.

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This work was supported financially by funding from TOTAL S.A., the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council of Canada, the CIFAR Bio-Inspired Solar Energy programme, a University of Toronto Connaught grant, the Ministry of Science, Natural Science Foundation of China (21471040, 21271055 and 21501035), the Innovation-Driven Plan in Central South University project (2017CX003), a project from State Key Laboratory of Powder Metallurgy in Central South University, the Thousand Youth Talents Plan of China and Hundred Youth Talents Program of Hunan and the China Scholarship Council programme. This work benefited from the soft X-ray microcharacterization beamline at CLS, sector 20BM at the APS and the Ontario Centre for the Characterisation of Advanced Materials at the University of Toronto. H.Y. acknowledges financial support from the Research Foundation-Flanders (FWO postdoctoral fellowship). C.Z. acknowledges support from the International Academic Exchange Fund for Joint PhD Students from Tianjin University. P.D.L. acknowledges financial support from the Natural Sciences and Engineering Research Council in the form of the Canada Graduate Scholarship—Doctoral award. S.B. and E.B. acknowledge financial support from the European Research Council (ERC Starting Grant #335078-COLOURATOMS). The authors thank B. Zhang, N. Wang, C. T. Dinh, T. Zhuang, J. Li and Y. Zhao for fruitful discussions, as well as Y. Hu and Q. Xiao from CLS, and Z. Finfrock and M. Ward from APS for their help during the course of study. Computations were performed on the SOSCIP Consortium’s Blue Gene/Q computing platform. 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: Yansong Zhou, Fanglin Che, Min Liu.


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

    • Yansong Zhou
    • , Fanglin Che
    • , Min Liu
    • , Chengqin Zou
    • , Zhiqin Liang
    • , Haifeng Yuan
    • , Jun Li
    • , Peining Chen
    • , Rafael Quintero-Bermudez
    •  & Edward H. Sargent
  2. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

    • Yansong Zhou
    •  & Gang Chen
  3. Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, China

    • Min Liu
    • , Haipeng Xie
    •  & Hongmei Li
  4. State Key Laboratory of Power Metallurgy, Central South University, Changsha, China

    • Min Liu
  5. Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

    • Phil De Luna
  6. Department of Chemistry, KU Leuven, Leuven, Belgium

    • Haifeng Yuan
    •  & Johan Hofkens
  7. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    • Jun Li
    •  & David Sinton
  8. Department of Chemistry, University of Western Ontario, London, Ontario, Canada

    • Zhiqiang Wang
    •  & Tsun-Kong Sham
  9. EMAT, University of Antwerp, Antwerp, Belgium

    • Eva Bladt
    •  & Sara Bals


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E.H.S. and G.C. supervised the project. Y.Z. and M.L. conceived the idea, designed the experiments and analysed the results. Y.Z. synthesized the samples, performed the electrochemical experiments and analysed the results. F.C. carried out the simulations and wrote the corresponding section. M.L., P.C. and P.D.L. conducted the XAS measurements. J.L., Z.W., T.-K.S. and D.S. assisted in analysing the XAS results. C.Z., Y.Z. and Z.L. ran the NMR tests. M.L. and C.Z. carried out the scanning electron microscope measurements. Y.Z. and H.Y. designed the ICP-OES experiments. C.Z. performed the ICP-OES tests. Z.L. ran the X-ray diffractometer tests. R.Q.-B., H.X. and H.L. performed the XPS measurements. E.B. conducted the TEM measurements. E.B., H.Y., S.B. and J.H. assisted in analysing the TEM results. All authors read and commented on the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Gang Chen or Edward H. Sargent.

Supplementary information

  1. Supplementary information

    Supplementary computational simulation methods and data, Supplementary Figures 1–42, Supplementary Tables 1–14

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