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Heterogeneous electrosynthesis of C–N, C–S and C–P products using CO2 as a building block

Nature Synthesis (2024)Cite this article

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Abstract

Electrochemical CO2 reduction (CO2R) provides a sustainable route to produce carbon-based fuels. This Review explores the expansion of the scope and impact of CO2R by coupling CO2 with heteroatomic co-reactants. The societal demand for C–X (C–N, C–S and C–P) bond-containing chemicals is evaluated, and current synthetic routes for C–X bonds are examined. Established routes for heteroatom coupling are then contrasted with electrosynthetic approaches that use CO2 as a building block, which are classified into three distinct categories: (1) surface–solution coupling, (2) co-reduction and (3) near-surface coupling. Within each category, key aspects of the catalyst, reactor and molecule-specific reactivity that enable the coupling pathway are examined. The Review is concluded with a forward-looking discussion of required developments in electrocatalytic chemistry and how computational tools may accelerate progress. Finally, we examine upcoming challenges in both system design and technoeconomics that need to be addressed as this technology matures.

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Fig. 1: Technological pathways and societal demand for C–X products.
Fig. 2: Surface–solution coupling strategy.
Fig. 3: Overview of the co-reduction strategy to form C–X bonds.
Fig. 4: Near-surface coupling synthetic route for C–X bonds.
Fig. 5: Possibilities for scope expansion.
Fig. 6: Precursors, possible pre-coupling intermediates, and their pathways towards C–N coupling.
Fig. 7: Electrochemical cell configurations for C–X coupling reactions.
Fig. 8: TEA analysis.

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Acknowledgements

N.K., J.L., M.M., H.B. and Y.Z. acknowledge NSERC for a Discovery Grant (RGPIN-2019-05927). A.S. and H.H. acknowledge NSERC for a Discovery Grant (RGPIN-2020-04960) and the Canada Research Chair (950-23288). G.G. acknowledges financial support from Queen’s University (Canada). C.-T.D. acknowledges financial support from NSERC, the Canada Foundation for Innovation (CFI) and Queen’s University.

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Authors and Affiliations

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

    Junnan Li, Morgan McKee, Hossein Bemana, Yuxuan Zhang & Nikolay Kornienko

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

    Hamed Heidarpour & Ali Seifitokaldani

  3. Department of Chemical Engineering, Queen’s University, Kingston, Ontario, Canada

    Guorui Gao & Cao-Thang Dinh

  4. Institute of Inorganic Chemistry, University of Bonn, Bonn, Germany

    Nikolay Kornienko

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  1. Junnan Li
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Contributions

J.L., Y.Z., M.M., H.B. and N.K. analysed the chemical aspects. A.S. and H.H. provided insight into DFT, TEA and LCA. G.G. and C.-T.D. overviewed the systems section and helped with TEA. All authors provided input on the complete manuscript.

Corresponding authors

Correspondence to Cao-Thang Dinh, Ali Seifitokaldani or Nikolay Kornienko.

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Nature Synthesis thanks Shaojun Guo, Hailiang Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary Information

Supplementary Fig. 1, Table 1 and TEA modelling,

Supplementary Data

Data for sensitivity analysis

Source data

Source Data Fig. 8

TEA modelling for formamide (8a), acetamide (8b), urea (8c), breakdown of production cost of chemicals (8d)

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Li, J., Heidarpour, H., Gao, G. et al. Heterogeneous electrosynthesis of C–N, C–S and C–P products using CO2 as a building block. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00530-8

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