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Abstract

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity1,2,3,4,5,6,7. Unfortunately, the reaction suffers from slow kinetics7,8 owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species9,10, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption11, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at −0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at −0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

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Acknowledgements

This work was supported by 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. B.Z. acknowledges funding from Shanghai Municipal Natural Science Foundation (14ZR1410200) and the National Natural Science Foundation of China (21503079). We thank X. Lan, P. Kanjanaboos, G. Walters, L. Levina, R. Wolowiec, D. Kopilovic, E. Palmiano, T. Burdyny and J. Tam from the University of Toronto for Au electron beam deposition, liquid products testing, AFM testing, TEM EELS measurements, discussions and additional aids during the course of study, Y. Tian from the King Abdullah University of Science and Technology for electrode preparation assistance, and M. Bajdich, L. D. Chen and K. Chan from Stanford University for advice on DFT calculations. This work has also benefited from the Spherical Grating Monochromator beamlines at the Canadian Light Source. DFT calculations were performed on the IBM BlueGene Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP).

Author information

Author notes

    • Min Liu
    • , Yuanjie Pang
    • , Bo Zhang
    •  & Phil De Luna

    These authors contributed equally to this work.

Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, 35 St George Street, Toronto, Ontario M5S 1A4, Canada

    • Min Liu
    • , Bo Zhang
    • , Oleksandr Voznyy
    • , Jixian Xu
    • , Xueli Zheng
    • , Cao Thang Dinh
    • , Fengjia Fan
    • , F. Pelayo García de Arquer
    • , Tina Saberi Safaei
    •  & Edward H. Sargent
  2. Department of Mechanical and Industrial Engineering, University of Toronto, 5 King’s College Road, Toronto, Ontario M5S 3G8, Canada

    • Yuanjie Pang
    • , Changhong Cao
    • , Tobin Filleter
    •  & David Sinton
  3. Department of Physics, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China

    • Bo Zhang
  4. Department of Materials Science and Engineering, University of Toronto, 184 College Street, Toronto, Ontario M5S 3E4, Canada

    • Phil De Luna
  5. Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China

    • Xueli Zheng
  6. Institute of Biomaterials and Biomedical Engineering, University of Toronto, 164 College Street, Toronto, Ontario M5S 3G9, Canada

    • Adam Mepham
    •  & Shana O. Kelley
  7. Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada

    • Anna Klinkova
    •  & Eugenia Kumacheva
  8. Department of Pharmaceutical Sciences, Leslie Dan Faculty of Pharmacy, University of Toronto, 144 College Street, Toronto, Ontario M5S 3M2, Canada

    • Shana O. Kelley
  9. Department of Biochemistry, University of Toronto, 1 King’s College Circle, Toronto, Ontario M5S 1A8, Canada

    • Shana O. Kelley

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Contributions

E.H.S., S.O.K. and D.S. supervised the project. M.L., Y.P. and B.Z. designed and carried out all the experiments and COMSOL simulations. P.D.L. and O.V. carried out the DFT simulation. All authors discussed the results and assisted during manuscript preparation.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Edward H. Sargent.

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DOI

https://doi.org/10.1038/nature19060

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