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Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics

Nature Catalysis volume 8, pages 46–57 (2025)Cite this article

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Abstract

Electrochemical interfaces between polymer electrolytes and electrodes are central to electrochemical devices in the global transition towards renewable energy. Here we show that the adsorption and desorption of sulfonates in Nafion on Pt(111) involve distinct elementary steps, with the latter proceeding through a coupled cation–electron transfer. Adsorbed sulfonates not only block a fraction of surface Pt sites but, more importantly, generate two additional types of surface adsorbate, OHNafion and ONafion, which exhibit distinct kinetic properties from adsorbed OH and O on bare Pt(111), respectively. The impact of the adsorption of sulfonate groups in Nafion on the activity of the oxygen reduction reaction (ORR) on Pt cannot be rationalized by existing thermodynamic descriptors. The reduced ORR activity on the Nafion-covered Pt(111) is caused by the kinetically hindered *O→*OH conversion and *OH reduction on sites close to adsorbed sulfonates.

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Fig. 1: Adsorption and desorption of sulfonate groups on Nafion-covered Pt(111).
Fig. 2: Coupled cation–electron transfer in sulfonate desorption.
Fig. 3: Isotopic labelling experiments.
Fig. 4: Non-Nernstian shift behaviour of the sulfonate adsorption peak.
Fig. 5: Identification of OHNafion and ONafion species.
Fig. 6: Kinetic properties of OHnormal and OHNafion.
Fig. 7: Impact of Nafion on ORR kinetics.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work is supported by the National Key R&D Program of China (no. 2021YFA1501003). M.L. acknowledges the support of the National Natural Science Foundation of China under grant no. 22379002, and X.C. acknowledges the support of the National Natural Science Foundation of China under grant no. 22278002. We thank X. Chen from Beijing Institute of Technology for technical assistance and useful discussions.

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Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Kaiyue Zhao, Xiaoxia Chang & Bingjun Xu

  2. Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Kaiyue Zhao, Xiaoxia Chang & Bingjun Xu

  3. School of Materials Science and Engineering, Peking University, Beijing, China

    Mingchuan Luo

  4. College of Chemistry, Fuzhou University, Fuzhou, China

    Yongfan Zhang

  5. Ordos Laboratory, Ordos, China

    Bingjun Xu

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  1. Kaiyue Zhao
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Contributions

K.Z., M.L. and B.X. conceived the idea and designed the experiments. K.Z. conducted the electrochemical measurements and in situ IR experiments. Y.Z. performed molecular dynamics simulations. X.C. conducted parts of the electrochemical measurements. K.Z., M.L., Y.Z. and B.X. analysed experimental and computational data, and co-wrote the paper, with input from all other co-authors.

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Correspondence to Mingchuan Luo or Bingjun Xu.

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Nature Catalysis thanks Chiyoung Jung, Kensaku Kodama and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–22, Tables 1–3, Notes 1–5 and refs. 1–12.

Supplementary Data 1

Atomic coordinates of calculation

Source data

Source Data Fig. 1

Adsorption and desorption of sulfonate groups on Nafion-covered Pt(111).

Source Data Fig. 2

Coupled cation-electron transfer in the sulfonate desorption.

Source Data Fig. 3

Isotopic labelling experiments.

Source Data Fig. 4

Non-Nernstian shift behaviour of the sulfonate adsorption peak.

Source Data Fig. 5

Identification of OHNafion and ONafion species.

Source Data Fig. 6

Kinetic properties of OHnormal and OHNafion.

Source Data Fig. 7

Impact of Nafion on the ORR activities.

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Zhao, K., Luo, M., Zhang, Y. et al. Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics. Nat Catal 8, 46–57 (2025). https://doi.org/10.1038/s41929-024-01279-1

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