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Selective and energy-efficient electrosynthesis of ethylene from CO2 by tuning the valence of Cu catalysts through aryl diazonium functionalization

Nature Energy volume 9, pages 422–433 (2024)Cite this article

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Abstract

Although progress has been made in producing multi-carbon products from the electrochemical reduction of CO2, the modest selectivity for ethylene (C2H4) leads to low energy efficiency and high downstream separation costs. Here we functionalize Cu catalysts with a variety of substituted aryl diazonium salts to improve selectivity towards multi-carbon products. Using computation and operando spectroscopy, we find that Cu surface oxidation state (δ+ where 0 < δ < 1) can be tuned by functionalization and that it influences the selectivity to C2H4. We report a Faradaic efficiency and a specific current density for C2H4 as large as 83 ± 2% and 212 mA cm−2, respectively, on partially oxidized Cu0.26+. Using a CO gas feed, we demonstrate an energy efficiency of ~40% with a C2H4 Faradaic efficiency of 86 ± 2%, corresponding to a low electrical power consumption of 25.6 kWh Nm−3 for the CO to C2H4 conversion reaction. Our findings provide a route towards practical electrosynthesis of C2H4 using valence engineering of copper.

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Fig. 1: DFT simulations.
Fig. 2: DFT calculations.
Fig. 3: Structural, compositional and CO2RR performance for the different Cu-X catalysts measured in MEA flow cells.
Fig. 4: Comparison of the selectivity, energy efficiency and electric power consumption.
Fig. 5: XAS, Auger and operando Raman characterizations.
Fig. 6: CO2-to-C2H4 performance in the cascade flow process.
Fig. 7: Techno-economic analyses for the CO2-to-C2H4 conversion based on the direct and the cascade flow processes.
Fig. 8: Comparison of operational costs.

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Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information. Source data are available at https://doi.org/10.6084/m9.figshare.24903033. Source data are provided with this paper.

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Acknowledgements

Support from the European Research Council is gratefully acknowledged, as is support from the European Union’s Horizon 2020 research and innovation programme (grant agreement number 804320) to D.V. This work was also financially supported by the Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality (grant agreement number BK20220023), as support to D.R. We thank the National Facility ELECMI ICTS (‘Division de Microscopia Electronica’, Universidad de Cadiz, DME-UCA) for the use of TEM instrumentation. We also acknowledge funding from the European Union’s Horizon 2020 research and innovation programme (grant agreement 823717-ESTEEM3) and the Spanish Ministerio de Economia y Competitividad (PID2019-107578GA-I00), the Ministerio de Ciencia e Innovación MCIN/AEI/10.13039/501100011033 and the European Union ‘NextGenerationEU’/PRTR (RYC2021-033764-I, CPP2021-008986), as support to L.L. We also acknowledge funding from the French National Agency (ANR, JCJC programme, MONOMEANR-20-CE08-0009), as support to C.S. We acknowledge M. Rüscher, F. T. Haase and L. Bai for their help on synchrotron tests. We also acknowledge SOLEIL for provision of synchrotron radiation facilities and we would like to thank A. Zitolo for assistance in using beamline SAMBA within the proposal 20200732. XAS experiments were also performed at CLAESS beamline at ALBA synchrotron with the collaboration of ALBA staff. P. Montels and D. Valenza are acknowledged for their technical assistance with the MEA cells.

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Authors and Affiliations

  1. Institut Européen des Membranes, IEM, UMR 5635, Université Montpellier, ENSCM, CNRS, Montpellier, France

    Huali Wu, Kun Qi, Wensen Wang, Jiefeng Liu, Yang Zhang, Eddy Petit, Chrystelle Salameh, Philippe Miele & Damien Voiry

  2. School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, People’s Republic of China

    Lingqi Huang

  3. Department of Interface Science, Fritz-Haber-Institute of the Max-Planck Society, Berlin, Germany

    Janis Timoshenko & Beatriz Roldán Cuenya

  4. School of Materials Science and Engineering, Jiangsu University, Zhenjiang, People’s Republic of China

    Shaokang Yang & Dewei Rao

  5. Institut Charles Gerhardt, ICGM, UMR 5253, University of Montpellier, ENSCM, CNRS, Montpellier, France

    Valérie Flaud

  6. College of Bioresources and Materials Engineering, Shanxi University of Science and Technology, Xi’an, People’s Republic of China

    Ji Li

  7. Institut Universitaire de France (IUF), Paris, France

    Philippe Miele

  8. Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de Cádiz, Cádiz, Spain

    Luc Lajaunie

  9. Instituto Universitario de Investigación de Microscopía Electrónica y Materiales (IMEYMAT), Facultad de Ciencias, Universidad de Cádiz, Cádiz, Spain

    Luc Lajaunie

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Contributions

D.V. conceived the idea and designed the experiments. D.R. performed the DFT calculations and discussed the results with D.V. and H.W. H.W. designed the experiments with D.V., prepared the electrodes and performed the electrochemical measurements. H.W., D.R. and D.V. analysed the data and wrote the manuscript. L.H. and V.F. performed the XPS and Auger measurements and analysed the data with H.W. J.T. and H.W. performed the ex situ and operando XAS measurements and analysed the data. L.L. performed HR-STEM, HR-TEM and EELS on the Cu-X catalysts and discussed the results with H.W., and D.V. and S.Y. performed DFT data collections and discussed the results with H.W. E.P. carried out the liquid NMR spectroscopy measurements. K.Q. and Y.Z. assisted H.W. with the electrochemical investigations and the gas chromatography analyses. W.W., J. Li and J. Liu assisted H.W. with the physical characterization of the samples and the operando Raman measurements. C.S. and P.M. discussed the electrocatalytic performance with H.W. and D.V. B.R.C. discussed the XAS data with J.T., H.W. and D.V. All authors discussed the results and assisted during manuscript preparation.

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Correspondence to Dewei Rao or Damien Voiry.

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Nature Energy thanks Tao Cheng and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–80, Tables 1–32, Methods, Notes 1–6 and Refs. 1–33.

Supplementary Data 1

Source data for Supplementary Figs. 31, 35, 51, 52a–c, 54, 65 and 72b,c.

Supplementary Data 2

The optimized computational models, the energy in the reaction.

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Source Data Fig. 5

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Source Data Fig. 6

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Source Data Fig. 7

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Source Data Fig. 8

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Wu, H., Huang, L., Timoshenko, J. et al. Selective and energy-efficient electrosynthesis of ethylene from CO2 by tuning the valence of Cu catalysts through aryl diazonium functionalization. Nat Energy 9, 422–433 (2024). https://doi.org/10.1038/s41560-024-01461-6

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