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Operando proton-transfer-reaction time-of-flight mass spectrometry of carbon dioxide reduction electrocatalysis

Nature Catalysis volume 5, pages 1169–1179 (2022)Cite this article

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Abstract

Electrochemical carbon dioxide reduction is a potential pathway for sustainable production of fuels and chemicals. However, the detailed catalytic mechanism in cells using high-current gas diffusion electrodes remains uncertain. Here we use proton-transfer-reaction time-of-flight mass spectrometry (PTR–TOF–MS) to perform operando analysis of intermediates and products generated by electrochemical carbon dioxide reduction in gas-diffusion-electrode-based flow cells with copper-based electrocatalysts. PTR–TOF–MS allows for sensitive detection of C1–C4 minor and major intermediates and products, measurement of their 13C isotope composition and precise identification of onset potentials. We find that formaldehyde and acetaldehyde are not the major intermediates for formation of methanol and ethanol/ethylene, respectively, and that propionaldehyde reduction is on the major pathway for 1-propanol formation. Interestingly, the discrimination against 13C in the reaction products is substantially larger than for biological CO2 fixation in photosynthesis and Fischer–Tropsch synthesis of hydrocarbons.

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Fig. 1: GDE and operando set-up.
Fig. 2: Identification of intermediates and products.
Fig. 3: Major formation pathways of C1 products.
Fig. 4: Operando measurement of C2 and C3 products.
Fig. 5: 13C fractionation in C2 and C3 products.
Fig. 6: Major formation pathways of C2 products.

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Data availability

The data and analyses for the figures in the main part of the manuscript are openly available at https://doi.org/10.5281/zenodo.7047052. All data in the study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Research Foundation (NRF), Prime Minister’s Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme through the eCO2EP project operated by Cambridge Centre for Advanced Research and Education in Singapore (CARES) and the Berkeley Education Alliance for Research in Singapore (BEARS). We thank E. Hartungen of IONICON for valuable technical advice on the operation of the PTR-MS instrument.

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Authors and Affiliations

  1. Cambridge Centre for Advanced Research and Education in Singapore Ltd, University of Cambridge, Singapore, Singapore

    Hangjuan Ren, Mikhail Kovalev, Marsha Zakir Muhamad, Yuan Sheng, Libo Sun, Jingjing Wang, Simon Rihm & Alexei A. Lapkin

  2. Department of Chemistry, University of Oxford, Oxford, UK

    Hangjuan Ren

  3. Department of Chemistry, University College London, London, UK

    Zhaoyue Weng

  4. School of Physics, UNSW Sydney, Sydney, NSW, Australia

    Hongyang Ma

  5. Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK

    Simon Rihm & Alexei A. Lapkin

  6. School of Materials Science and Engineering, Shandong University, Jinan, China

    Wanfeng Yang

  7. Materials and Chemical Sciences Divisions, Lawrence Berkeley National Laboratory and Department of Materials Science and Engineering, University of California Berkeley, Berkeley, CA, USA

    Joel W. Ager

  8. Berkeley Educational Alliance for Research in Singapore Center, University of California, Berkeley, Singapore

    Joel W. Ager

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Contributions

H.R. conceptualized the study, developed the methodology and software, performed experiments, analysed and validated data, wrote the original draft of manuscript and revised the manuscript. M.K. developed the methodology, performed experiments, analysed and validated data and reviewed the manuscript. Z.W. performed DFT calculations with assistance from H.M. and wrote the DFT parts of the manuscript. M.Z.M., Y.S., L.S., J.W. and W.Y. assisted in experiments. S.R. contributed to mechanism analysis. A.A.L. acquired funding, supervised the project and reviewed the manuscript. J.W.A. conceptualized the study, acquired funding, developed the methodology and software, administered the project, supervised the project and reviewed and edited the manuscript.

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Correspondence to Alexei A. Lapkin or Joel W. Ager.

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Nature Catalysis thanks Leanne Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Notes 1–5, Figs. 1–28 and Tables 1–10.

Supplementary Data 1

Atomic coordinates of intermediates and products used in DFT calculations.

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Ren, H., Kovalev, M., Weng, Z. et al. Operando proton-transfer-reaction time-of-flight mass spectrometry of carbon dioxide reduction electrocatalysis. Nat Catal 5, 1169–1179 (2022). https://doi.org/10.1038/s41929-022-00891-3

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