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Selective synthesis of butane from carbon monoxide using cascade electrolysis and thermocatalysis at ambient conditions

Nature Catalysis volume 6, pages 310–318 (2023)Cite this article

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Abstract

It is of interest to extend the reach of CO2 and CO electrochemistry to the synthesis of products with molecular weights higher than the C1 and C2 seen in most prior reports carried out near ambient conditions. Here we present a cascade C1–C2–C4 system that combines electrochemical and thermochemical reactors to produce C4H10 selectively at ambient conditions. In a C2H4 dimerization reactor, we directly upgrade the gas outlet stream of the CO2 or CO electrolyser without purification. We find that CO, which is present alongside C2H4, enhances C2H4 dimerization selectivity to give C4H10 to 95%, a much higher performance than when a CO2 electrolyser is used instead. We achieve an overall two-stage CO-to-C4H10 cascade selectivity of 43%. Mechanistic investigations, complemented by density functional theory calculations reveal that increased CO coverage favours C2H4 dimerization and hydrogenation of *CxHy adsorbates, as well as destabilizes the *C4H9 intermediate, and so promotes the selective production of the target alkane.

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Fig. 1: Conventional pathway and cascade system for C4 hydrocarbon production.
Fig. 2: Mechanistic insights into highly selective C4H10 generation.
Fig. 3: Cascade systems for C4 hydrocarbon production.
Fig. 4: Performance of cascade eCO-to-C4 system.
Fig. 5: Carbon footprint and energy assessment for C4 production.

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Data availability

Source data are provided with this paper. All other data that support the findings of this study are provided with the paper and its Supplementary Information files. All the data in the study are available from the corresponding author upon reasonable request.

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Acknowledgements

All DFT calculations were performed on the Niagara supercomputer of the SciNet HPC Consortium. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, Ontario Research Fund Research Excellence Program and the University of Toronto. M.G.L. acknowledges the Basic Science Research Program through the NRF funded by the Ministry of Education (2021R1A6A3A03039988). J.W.Y. acknowledges the Basic Science Research Program through the NRF funded by the Ministry of Education (2021R1A6A3A13046700).

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Author notes

  1. These authors contributed equally: Mi Gyoung Lee, Xiao-Yan Li, Adnan Ozden, Joshua Wicks.

Authors and Affiliations

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

    Mi Gyoung Lee, Xiao-Yan Li, Joshua Wicks, Pengfei Ou, Yuhang Li, Roham Dorakhan, Bin Chen, Jehad Abed, Geonhui Lee, Jianan Erick Huang, Tao Peng & Edward H. Sargent

  2. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Adnan Ozden & David Sinton

  3. Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario, Canada

    Jaekyoung Lee & Ya-Huei (Cathy) Chin

  4. Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul, Republic of Korea

    Hoon Kee Park & Jin Wook Yang

  5. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Roberto dos Reis

  6. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Edward H. Sargent

  7. Department of Electrical and Computer Engineering, Northwestern University, Evanston, IL, USA

    Edward H. Sargent

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Contributions

M.G.L. designed the project, performed most of the experiments on C2H4 dimerization and C1–C2–C4 cascade systems. X.-Y.L. and P.O. performed the DFT calculations. A.O. fabricated the electrodes for eCORR and analysed the energy cost. J.W. contributed the carbon footprint analysis. Y.L. and J.E.H. contributed the system design. R.D., J.L. and Y-.H.C. participated in the chemisorption analysis. J.A. performed the X-ray diffraction analysis. H.K.P. conducted the XPS and FTIR analyses. J.W.Y. participated in the scanning electron microscopy and energy-dispersive X-ray spectroscopy analysis. B.C. participated in the transmission electron microscopy analysis. G.L. contributed to the FTIR analysis and GC measurement. T.P. contributed to the GC–MS analysis. D.S. and E.H.S. supervised the project. M.G.L., X.-Y.L., A.O. and J.W. wrote and revised the manuscript. All the authors discussed the results and commented on the manuscript at all stages.

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Correspondence to Edward H. Sargent.

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Nature Catalysis thanks Alexander Mitsos, Feng Jiao, Gonzalo Prieto and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–16, Tables 1–10, Notes 1–9 and references.

Supplementary Data 1

DFT calculations of Fig. 2c and Supplementary Figs. 5 and 6.

Source data

Source Data Fig. 2

Data points as displayed in Fig. 2a,b.

Source Data Fig. 3

Data points as displayed in Fig. 3b,e,f.

Source Data Fig. 4

Data points as displayed in Fig. 4a–f.

Source Data Fig. 5

Data points as displayed in Fig. 5a,b.

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Lee, M.G., Li, XY., Ozden, A. et al. Selective synthesis of butane from carbon monoxide using cascade electrolysis and thermocatalysis at ambient conditions. Nat Catal 6, 310–318 (2023). https://doi.org/10.1038/s41929-023-00937-0

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