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Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations

Nature Catalysis volume 7, pages 689–701 (2024)Cite this article

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Abstract

Electrochemical carbon dioxide reduction (CO2R) can provide a sustainable route to produce fuels and chemicals; however, CO2R selectivity is frequently impaired by the competing hydrogen evolution reaction (HER), even for small concentrations of water. Here we tune water solvation and dynamics within a series of aprotic solvents featuring different functional groups and physicochemical properties to modulate HER activity and CO2R selectivity. We show that one can extend the HER onset potential by almost 1 V by confining water within a strong hydrogen bond network. We then achieve nearly 100% CO Faradaic efficiency at water concentrations as high as 3 M with a gold catalyst. Furthermore, under mildly acidic conditions, we sustain nearly 100% Faradaic efficiency towards CO with no carbonate losses over long-term electrolysis with an earth-abundant zinc catalyst. Our work provides insights to control water’s reactivity and reveals descriptors to guide electrolyte design for important electrochemical transformations.

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Fig. 1: Water speciation in organic media.
Fig. 2: Water clustering and dynamics.
Fig. 3: Influence of water solvation on HER.
Fig. 4: Influence of water addition on CO2R.
Fig. 5: Effect of water solvation on kinetics.
Fig. 6: Electrochemistry under acidic conditions.

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Data availability

Molecular dynamics inputs, initial and final configurations, and optimized structures for DFT calculations are provided in the Supplementary Information or are available online at https://github.com/AmanchukwuLab/water_activity_aprotic_CO2R_HER (ref. 69). The data supporting the findings of this study are available within the article and its Supplementary Information, or can be obtained from the corresponding author on reasonable request.

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Acknowledgements

This work was primarily supported by the U.S. Department of Energy Office of Science Basic Energy Sciences, Early Career Research Program (DE-SC0024103). C.V.A. was supported by the CIFAR Azrieli Global Scholars Program. R.J.G. was partially supported by the Roberto Rocca Scholars Program. R.K. was supported by the Eric and Wendy Schmidt AI in Science Postdoctoral Fellowship. H.F. was supported by the National Science Foundation Graduate Research Fellowship Program. I.R. was supported by the UChicago Quad Scholars Program. We thank N.H.C. Cohen and A. Tokmakoff for insightful discussions, and C. Vu for the scanning electron microscopy images. This work made use of the shared facilities (Raman) at the University of Chicago Materials Research Science and Engineering Center, supported by the National Science Foundation under award no. DMR-2011854. Fourier-transform infrared was performed at the Soft Matter Characterization Facility of the University of Chicago. Solution-state NMR measurements were performed at the UChicago Chemistry NMR Facility. Molecular dynamics and DFT calculations were performed with resources provided by the University of Chicago’s Research Computing Center.

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  1. Pritzker School of Molecular Engineering, The University of Chicago, Chicago, IL, USA

    Reginaldo J. Gomes, Ritesh Kumar, Hannah Fejzić, Bidushi Sarkar, Ishaan Roy & Chibueze V. Amanchukwu

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  1. Reginaldo J. Gomes
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Contributions

R.J.G. and C.V.A. conceptualized the paper. R.J.G. was responsible for the methodology and carried out the investigation. R.K. performed the MD and DFT calculations. H.F. performed experimental validation. I.R. performed NMR characterization. B.S. performed electrolyte stability analysis. R.J.G. and C.V.A. wrote the manuscript and all co-authors contributed to editing. C.V.A. supervised the work.

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Correspondence to Chibueze V. Amanchukwu.

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Supplementary Notes 1–7, Figs. 1–18, Tables 1–9 and refs. 1–33.

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Gomes, R.J., Kumar, R., Fejzić, H. et al. Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations. Nat Catal 7, 689–701 (2024). https://doi.org/10.1038/s41929-024-01162-z

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