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Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium

Nature Catalysis volume 5, pages 268–276 (2022)Cite this article

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Abstract

The reaction of carbon dioxide with hydroxide to form carbonate in near-neutral or alkaline medium severely limits the energy and carbon efficiency of CO2 electroreduction. Here we show that by suppression of the otherwise predominant hydrogen evolution using alkali cations, efficient CO2 electroreduction can be conducted in acidic medium, overcoming the carbonate problem. The cation effects are general for three typical catalysts including carbon-supported tin oxide, gold and copper, leading to Faradaic efficiency as high as 90% for formic acid and CO formation. Our analysis suggests that hydrated alkali cations physisorbed on the cathode modify the distribution of electric field in the double layer, which impedes hydrogen evolution by suppression of migration of hydronium ions while at the same time promoting CO2 reduction by stabilization of key intermediates.

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Fig. 1: Performance of CO2 reduction in acidic solutions containing K+ ions.
Fig. 2: Comparison of CO2 electroreduction in acidic, near-neutral and alkaline media.
Fig. 3: Estimation of energy consumption for sustainable CO2 electroreduction.
Fig. 4: Cation effects on HER and CO2 reduction.
Fig. 5: Cation effects on electric field distribution.
Fig. 6: Simulation of local pH effect.

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Data availability

Data that support the findings of this study can be found in the article and the Supplementary information. Source data are available from the corresponding author upon request. Datasets for Figs. 1–6 can be found in Zenodo53.

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Acknowledgements

We thank L. Bai for help with TEM characterizations, and H. Qin for help with XPS characterization and RDE tests. This work was supported by the European Research Council (no. 681292 to X.H), NCCR Catalysis (no. 180544 to X.H. and S.H.), a National Centre of Competence in Research funded by the Swiss National Science Foundation, the EPFL (X.H. and S.H.), Foundation of Shenzhen Science, Technology and Innovation Commission (no. JCYJ20210324104414039 to J.G.), the European Union Marie Sklodowska-Curie Individual Fellowships (no. 891545 to W.R.), the European Union’s Horizon 2020 research and innovation programme (no. 85144, SELECT-CO2, to S.H.) and a Starting Grant of the Swiss National Science Foundation (no. 155876 to S.H.).

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Authors and Affiliations

  1. Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Jun Gu, Weiyan Ni, Wenhao Ren & Xile Hu

  2. Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Jun Gu

  3. Laboratory of Renewable Energy Science and Engineering, Institute of Mechanical Engineering, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Shuo Liu & Sophia Haussener

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Contributions

J.G. performed the majority of synthesis, characterization and electrochemical tests. S.L. performed simulations. W.N. performed Au RDE tests. W.R. performed electrochemical tests in near-neutral and alkaline media. J.G., S.L., S.H. and X.H. analysed data. J.G. and X.H. wrote the paper, with input from all other co-authors. S.H. and X.H. directed the research.

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Correspondence to Xile Hu.

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Supplementary Information

Supplementary methods, Notes 1 and 2, Figs. 1–26, Tables 1–4 and references.

Supplementary Video 1

RDE experiment. Au RDE in 0.1 M HOTf + 0.4 M KOTf. Current density was –200 mA cm–2 and rotating speed was 1,600 r.p.m.

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Gu, J., Liu, S., Ni, W. et al. Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium. Nat Catal 5, 268–276 (2022). https://doi.org/10.1038/s41929-022-00761-y

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