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Electrochemical formation of C–S bonds from CO2 and small-molecule sulfur species

Nature Synthesis volume 2, pages 757–765 (2023)Cite this article

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Abstract

The formation of C–S bonds is an important step in the synthesis of pharmaceutical, biological and chemical products. Electrocatalysis using abundant precursors is an attractive and green route to C–S bond-containing species, but examples within this context are largely absent from the literature. To this end, this work demonstrates the use of CO2 and SO32− as cheap building blocks that couple on the surface Cu-based heterogeneous catalysts. Hydroxymethanesulfonate, sulfoacetate and methanesulfonate are formed, with Faradaic efficiencies of up to 6.8%. A combination of operando measurements and computational modelling reveal that the *CHOH intermediate formed on metallic Cu is a key electrophilic species that is nucleophilically attacked by SO32− in the principal C–S bond-forming step. The proof-of-concept for electrocatalytic C–S bond formation and mechanistic insights gained will broaden the scope of the emerging field of electrosynthesis.

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Fig. 1: Concept of electrochemical C–S coupling.
Fig. 2: Electrochemical synthesis of C–S products.
Fig. 3: Analysis of catalyst and reaction dynamics.
Fig. 4: Modelling of possible reaction pathways from CO to HMS.
Fig. 5: Energy diagram on Cu (100).
Fig. 6: Expanded scope of C–S coupling.

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Data availability

All data will be deposited in ChemRxiv, a publicly accessible repository (https://chemrxiv.org/engage/chemrxiv/article-details/6397d9a0cfb5ff102468e064).

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Acknowledgements

N.K. and J. L. acknowledge the NSERC for its Discovery Grant RGPIN-2019-05927. A.S. acknowledges the NSERC for its Discovery Grant RGPIN-2020-04960 and Canada Research Chair (950-23288). The computations in this research were enabled in part by support provided by Calcul Quebec and Compute Canada.

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Author notes

  1. These authors contributed equally: Junnan Li, Hasan Al-Mahayni.

Authors and Affiliations

  1. Department of Chemistry, Université de Montréal, Montréal, Québec, Canada

    Junnan Li, Daniel Chartrand & Nikolay Kornienko

  2. Department of Chemical Engineering, McGill University, Montréal, Québec, Canada

    Hasan Al-Mahayni & Ali Seifitokaldani

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  1. Junnan Li
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Contributions

J.L., D.C. and N.K. carried out electrochemical and operando studies. H.A.-M. and A.S. carried out computational work. All authors contributed to analysis and to the manuscript.

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Correspondence to Ali Seifitokaldani or Nikolay Kornienko.

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Nature Synthesis thanks H. Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended methods description and Supplementary figs. 1–41.

Source data

Source Data Fig. 2

Unprocessed data of: NMR spectra for standards and reaction solution (a), linear scan voltammetry traces (b), FE for products (c,d) and partial current density (e).

Source Data Fig. 3

Potential and time-dependent XRD and Raman spectra.

Source Data Fig. 5

Energies of reaction intermediates in the calculated free energy landscape.

Source Data Fig. 6

Raw values of product formation rates.

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Li, J., Al-Mahayni, H., Chartrand, D. et al. Electrochemical formation of C–S bonds from CO2 and small-molecule sulfur species. Nat. Synth 2, 757–765 (2023). https://doi.org/10.1038/s44160-023-00303-9

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