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Electroreduction-driven distorted nanotwins activate pure Cu for efficient hydrogen evolution

Nature Materials volume 24, pages 424–432 (2025)Cite this article

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Abstract

Precious metals such as Pt are favoured as catalysts for the hydrogen evolution reaction (HER) due to their excellent catalytic activity. However, the scarcity and high cost of precious metals have prompted researchers to explore cheaper alternatives such as Cu. Nevertheless, Cu shows poor catalytic performance due to weak binding with intermediates. Here the catalytic activity of pure Cu is activated via electroreduction-driven modification of the local structure, achieving a HER catalytic performance superior to commercial Pt/C catalysts for working current densities greater than 100 mA cm−2 in acid electrolyte. Activation involved two steps. First, polycrystalline Cu2O nanoparticles were prepared via pulsed laser ablation, resulting in grain boundaries within the Cu2O particles as observed using electron microscopy. Next, the Cu2O particles were electroreduced to pure Cu, inducing the formation of distorted nanotwins and edge dislocations. These local structures induce high lattice strain and decrease the Cu coordination number, enhancing the interaction between Cu and intermediates—as calculated using density functional theory—leading to the excellent catalytic activity and durability of the catalyst. Our observations show that low-cost pure Cu can be a promising HER catalyst for large-scale industrial applications.

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Fig. 1: Preparation and characterization of DNTs-Cu catalysts.
Fig. 2: Analyses on the origin of lattice strain in DNTs-Cu.
Fig. 3: 3D atomic structure and 3D strain tensor measurements in a DNTs-Cu particle.
Fig. 4: HER activity and durability of different catalysts in an argon-saturated 0.5 M H2SO4 aqueous electrolyte.

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All data that support the findings of this work are available within the Article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

F.F. gratefully acknowledges funding support from the National Key R&D Program of China (2020YFA0406204), the National Natural Science Foundation of China (no. 52071083) and the Zhuhai Fudan Innovation Institute. Z.L. gratefully acknowledges funding support from the National Natural Science Foundation of China (no. 52401292), the Postdoctoral Innovation Talents Support Program of China (BX2021066) and the China Postdoctoral Science Foundation (no. 2021M700024). Y. Lu gratefully acknowledges funding support from the National Natural Science Foundation of China (nos. 12074016 and 12274009), the Beijing Natural Science Foundation for Outstanding Youth Science Foundation (JQ24009) and the Research and Development Project from the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SX-TD001). J.Z. gratefully acknowledges funding support from the National Natural Science Foundation of China (no. 22172003) and strong support from the Electron Microscopy Laboratory at Peking University for the use of aberration-corrected electron microscopes and the High-performance Computing Platform of Peking University. We thank R. Che from Fudan University for charge distribution testing.

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  1. These authors contributed equally: Zhe Li, Yueshuai Wang, Hui Liu.

Authors and Affiliations

  1. Department of Materials Science, Fudan University, Shanghai, China

    Zhe Li, Yang Liu, Yun Song, Fei Wang, Fang Fang & Dalin Sun

  2. Institute of Molecular Plus, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Zhe Li

  3. Beijing Key Lab of Microstructure and Property of Advanced Materials, College of Materials Science and Engineering, Beijing University of Technology, Beijing, China

    Yueshuai Wang, Manling Sui & Yue Lu

  4. Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, China

    Hui Liu, Yi Feng & Xiwen Du

  5. Beijing National Laboratory for Molecular Sciences, Center for Integrated Spectroscopy, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Zhiheng Xie & Jihan Zhou

  6. School of Materials Science and Engineering, Anhui University, Hefei, China

    Fei Wang, Fang Fang & Dalin Sun

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Contributions

D.S. and F.F. conceived the experiments and supervised the project. Z.L. and Y.F. designed and conducted the experiments. Z.L., H.L., Y. Liu, Y.S. and F.W. performed the experimental data analysis. Z.L., Y. Lu and F.F. wrote the paper. Y.W., Y. Lu and M.S. performed atomic-scale TEM measurements and analysed the data. J.Z. and Z.X. performed the atomic-resolution electron tomography experiments and 3D structural analysis. X.D., M.S. and D.S. contributed the experimental platform. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Jihan Zhou, Yue Lu, Fang Fang or Dalin Sun.

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Nature Materials thanks Mingshang Jin 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. 1–49, Tables 1–3 and Refs. 1–27.

Supplementary Data 1

The atomic coordinates of computational models.

Source data

Source Data Fig. 1

XAS data plotted in Fig. 1e,f.

Source Data Fig. 2

Atomic distance data plotted in Fig. 2c.

Source Data Fig. 3

Radial distribution function and statistical data plotted in Fig. 3d,k.

Source Data Fig. 4

Electrochemical data plotted in Fig. 4a–h.

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Li, Z., Wang, Y., Liu, H. et al. Electroreduction-driven distorted nanotwins activate pure Cu for efficient hydrogen evolution. Nat. Mater. 24, 424–432 (2025). https://doi.org/10.1038/s41563-024-02098-2

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