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Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface

Nature Materials volume 18, pages 1222–1227 (2019)Cite this article

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Abstract

The aqueous electrocatalytic reduction of CO2 into alcohol and hydrocarbon fuels presents a sustainable route towards energy-rich chemical feedstocks. Cu is the only material able to catalyse the substantial formation of multicarbon products (C2/C3), but competing proton reduction to hydrogen is an ever-present drain on selectivity. Here, a superhydrophobic surface was generated by 1-octadecanethiol treatment of hierarchically structured Cu dendrites, inspired by the structure of gas-trapping cuticles on subaquatic spiders. The hydrophobic electrode attained a 56% Faradaic efficiency for ethylene and 17% for ethanol production at neutral pH, compared to 9% and 4% on a hydrophilic, wettable equivalent. These observations are assigned to trapped gases at the hydrophobic Cu surface, which increase the concentration of CO2 at the electrode–solution interface and consequently increase CO2 reduction selectivity. Hydrophobicity is thus proposed as a governing factor in CO2 reduction selectivity and can help explain trends seen on previously reported electrocatalysts.

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Fig. 1: CO2 reduction as a source of sustainable fuel and an introduction to the plastron effect.
Fig. 2: Characterization of the electrode surface.
Fig. 3: The effect of hydrophobicity on electrocatalytic CO2 reduction.
Fig. 4: The proposed role of hydrophobicity in promoting CO2 reduction over proton reduction.

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Data availability

Raw data used in preparation of this manuscript is available to download at https://doi.org/10.7910/DVN/DSPZHE.

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Acknowledgements

V.M. acknowledges financial support from CNRS-Cellule Energie and Fondation of Collège de France for the acquisition of the GC equipment. D.W. was supported by an Idex PSL grant (ANR-10-IDEX-001-02 PSL), the Fondation du Collège de France and the Marie Curie PRESTIGE Fellowship programme. S.L. was funded by the Corps des Ponts, des Eaux et des Forêts. X-ray diffraction measurements were carried out by G. Rousse at the Collège de France. SEM images were collected by D. Montero at the Institut des Matériaux de Paris and F. Pillier at the Laboratoire Interfaces et Systèmes Electrochimiques. BET measurements were carried by J. Blanchard at the Laboratoire de Réactivité de Surface at Sorbonne Université.

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Author notes

  1. Victor Mougel

    Present address: Department of Chemistry and Applied Biosciences, Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology Zürich, Zürich, Switzerland

Authors and Affiliations

  1. Laboratoire de Chimie des Processus Biologiques, CNRS UMR 8229, Collège de France, Paris, France

    David Wakerley, Sarah Lamaison, Marc Fontecave & Victor Mougel

  2. Laboratoire de Physique de la Matière Condensée, CNRS-École Polytechnique, Palaiseau Cédex, France

    François Ozanam

  3. Sorbonne Université, UMR CNRS 7590, MNHN, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, IMPMC, Paris, France

    Nicolas Menguy

  4. Physical Chemistry of Surfaces Group, ChimieParisTech-CNRS, Institut de Recherche de Chimie Paris, Paris, France

    Dimitri Mercier & Philippe Marcus

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Contributions

D.W., M.F. and V.M. conceived the research. D.W. and S.L. performed electrocatalysis and characterization. N.M. carried out TEM measurements. F.O., S.L. and D.W. carried out the infrared experiments. XPS was carried out by D.M. and P.M. All authors the analysed the data. D.W. wrote the manuscript. S.L., M.F. and V.M. added to the discussion and contributed to the preparation of the manuscript. M.F. and V.M. supervised the work.

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Correspondence to Marc Fontecave or Victor Mougel.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–21 and Supplementary Tables 1–6.

Supplementary Video 1

Capture and retention of a gaseous CO2 stream by the hydrophobic Cu dendrite.

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Wakerley, D., Lamaison, S., Ozanam, F. et al. Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface. Nat. Mater. 18, 1222–1227 (2019). https://doi.org/10.1038/s41563-019-0445-x

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