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The role of ruthenium in improving the kinetics of hydrogen oxidation and evolution reactions of platinum

Abstract

Modifying Pt surfaces by foreign metals with a higher oxophilicity is a promising approach to improve the kinetics of hydrogen evolution and oxidation reactions. The role of foreign metals, however, is not fully understood. Here we study Ru-modified Pt as a model system to understand the underlying mechanisms in activity improvement through combining in situ infrared spectroscopy and theoretical calculations. In an alkaline solution, the hydrogen evolution and oxidation reaction activity of Ru-modified Pt is proportional to the Ru coverage due to the strain and electronic effects of the Pt substrate, which lower the energy barrier of the rate-determining Volmer step; these are the governing reasons for the improved catalytic activities. This work not only deepens our understanding of hydrogen electrocatalysis mechanisms, but also provides guidelines for the rational design of advanced electrocatalysts.

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Fig. 1: Electrochemical responses of Pt and Ru-modified Pt electrodes.
Fig. 2: In situ ATR-SEIRAS spectra.
Fig. 3: Ru coverage and activity relationship.
Fig. 4: DFT calculations of the HER on Pt(111) and Ru/Pt(111).

Data availability

The data that support the findings of this study are available within the article and its Supplementary Information files or from the corresponding author upon reasonable request. The atomic coordinates of the optimized models are provided in Supplementary Data 1. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Research Grant Council (16308420, 16310419 and C6011-20G, received by M.S.) of the Hong Kong Special Administrative Region, Hong Kong Branch of Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou) (SMSEGL20SC01, received by M.S.), Hong Kong Innovation and Technology Commission (ITC-CNERC14EG03, received by M.S.), Opening Project of the State Key Laboratory of Physical Chemistry of Solid Surfaces at Xiamen University (201903, received by M.S.) collaborated with B. Ren, the Tianhe-2 National Supercomputer Center in Guangzhou and the Research Grants Council Postdoctoral Fellowship Scheme (PDFS2021-6S08, received by S.Z.). The authors thank L. Weng from HKUST for fruitful discussions, and N. Ho from MCPF of HKUST for XPS measurements.

Author information

Authors and Affiliations

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Contributions

M.S. supervised the project. S.Z. and M.S. conceived the idea and designed the experiments. S.Z. performed the electrochemical and spectroscopic measurements. X.Q. carried out the simulations. S.Z., F.X., Z.T., J.L. and J.Y. performed the material preparation and general characterizations. Y.X. and Q.C. conducted the atomic force microscopy characterizations. S.Y. and M.C. performed the high-sensitivity low-energy ion scattering measurements. S.Z., X.Q. and M.S. analysed the data and wrote the manuscript. All the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Minhua Shao.

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Peer review information Nature Catalysis thanks Eduardo Gracia-Espino 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. 1–14, Discussion and Tables 1–4.

Supplementary Data 1

Atomic coordinates of the optimized models.

Source data

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Statistical Source Data.

Source Data Fig. 2

Statistical Source Data.

Source Data Fig. 3

Statistical Source Data.

Source Data Fig. 4

Statistical Source Data.

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Zhu, S., Qin, X., Xiao, F. et al. The role of ruthenium in improving the kinetics of hydrogen oxidation and evolution reactions of platinum. Nat Catal 4, 711–718 (2021). https://doi.org/10.1038/s41929-021-00663-5

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