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Synthesis of 4H-phase high-entropy alloys for electrocatalysis

Nature Materials (2026)Cite this article

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Abstract

High-entropy alloy (HEA) nanomaterials are promising catalysts for proton exchange membrane water electrolysers (PEMWE), yet their crystalline structures have typically been restricted to thermodynamically stable phases. Here, using Au nanomaterials with distinct crystal phases as templates, we synthesize and stabilize Au@HEA core–shell nanostructures through a general and robust wet-chemical method in which the HEA is composed of up to ten metallic elements (Ir, Pt, Ni, Fe, Co, Rh, Pd, Ru, Cu and Mn). Phase-dependent water electrolysis is demonstrated as a proof-of-concept application. The hexagonal close-packed 4H-Au@4H-IrPtNiFeCo catalyst exhibits superior activity and stability for the acidic hydrogen evolution reaction, oxygen evolution reaction and overall water electrolysis compared with the conventional face-centred cubic IrPtNiFeCo catalyst. In a PEMWE at 60 °C, the 4H-Au@4H-IrPtNiFeCo catalyst achieves 3,000 mA cm−2 at only 1.90 V and maintains stable operation for over 1,200 h at 1,000 and 2,000 mA cm−2, with degradation rates of ~6.3 and ~15.7 µV h−1, respectively. This work offers a strategy for designing highly efficient and stable HEA catalysts with tailored phases for future practical water electrolysis.

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Fig. 1
Fig. 2: Structural characterization of the 4H-Au@4H-IrPtNiFeCo core–shell NWs.
Fig. 3: Structural characterization of 4H-Au@4H-HEA core–shell NWs.
Fig. 4: Phase-dependent electrocatalytic performance and in situ XAS measurement of HEA catalysts.
Fig. 5: Measurement of overall water electrolysis using HEA catalysts.

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Data availability

All data that support the findings of this study are available from the corresponding author upon request.

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Acknowledgements

H.Z. is grateful for support from the Research Grants Council (RGC) of Hong Kong (GRF project no. 11307724, TRS (T23-713/22-R) – Carbon Neutrality), ITF project (ref. GHP/102/22SZ), Croucher Foundation (Croucher Senior Research Fellowship), the Start-Up Grant (project no. 9380100) and the grants (project nos. 9610663, 7020103 and 1886921) from the City University of Hong Kong, ITC via Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM). Y.Z. is grateful for financial support from the RGC of Hong Kong (GRF project no. 15307522) and The Hong Kong Polytechnic University (grant no. W36G). B.H. is grateful for support from the RGC of Hong Kong (15304023, 15304724 and C1003-23Y), the NSFC/RGC Joint Research Scheme (N_PolyU502/21) and the NSFC/RGC Collaborative Research Scheme (CRS_PolyU504/22). Z.L. and L.Z. gratefully acknowledge the support of fellowship awards from the RGC of Hong Kong (project nos. CityU JRFS2526-1S06 and JRFS2526-1S13). We thank the Shanghai Synchrotron Radiation Facility of BL14W1 (https://cstr.cn/31124.02.SSRF.BL14W1) for assistance with the XAFS measurements.

Author information

Author notes

  1. These authors contributed equally: Zijian Li, An Zhang, Changsheng Chen, Hua Yang, Mingzi Sun.

Authors and Affiliations

  1. Department of Chemistry, City University of Hong Kong, Hong Kong, China

    Zijian Li, An Zhang, Hua Yang, Mingzi Sun, Li Zhai, Xinyue Long, Lujiang Li, Wei Zhai, Zhenyu Shi, Zhiying Wu, Yiyao Ge, Yuhui Tian, Shuai Bi, Jie Wang, Zhiqi Huang, Bo Chen, Lixin Wang, Bolong Huang & Hua Zhang

  2. Department of Applied Physics, Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, China

    Changsheng Chen, Kuan Liang & Ye Zhu

  3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Qinghua Zhang

  4. Institute of Sustainability for Chemicals, Energy and Environment (ISCE2), A*STAR (Agency for Science, Technology and Research), Singapore, Singapore

    Shibo Xi

  5. Key Laboratory of Fluid and Power Machinery of Ministry of Education, School of Materials Science and Engineering, Xihua University, Chengdu, China

    Jie Wang

  6. Department of Chemistry, Institute of Major Scientific Facilities for New Materials, Guangdong Provincial Key Laboratory of Sustainable Biomimetic Materials and Green Energy, Southern University of Science and Technology, Shenzhen, China

    Shiqi Li & Zhen-Yu Wu

  7. Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Cailing Chen & Yu Han

  8. School of Emergent Soft Matter, South China University of Technology, Guangzhou, China

    Yu Han

  9. Electron Microscopy Center, South China University of Technology, Guangzhou, China

    Yu Han

  10. Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing, China

    Lin Gu

  11. Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Panzhe Qiao

  12. Hong Kong Institute for Clean Energy, City University of Hong Kong, Hong Kong, China

    Hua Zhang

  13. Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Hong Kong, China

    Hua Zhang

  14. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China

    Hua Zhang

  15. Shenzhen Research Institute, City University of Hong Kong, Shenzhen, China

    Hua Zhang

Authors
  1. Zijian Li
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  2. An Zhang
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  3. Changsheng Chen
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Contributions

H.Z. proposed the research direction and conceived and supervised the project. Z.L. designed and performed the experiments. Z.L. and H.Y. synthesized the materials. Z.L. and A.Z. carried out the electrochemical measurements. Changsheng Chen, Q.Z., K.L., Cailing Chen, B.C., Y.H., L.G. and Y.Z. collected the aberration-corrected STEM images and EDS elemental mapping. M.S. and B.H. performed the theoretical calculations and analysis. P.Q. and S.X. performed the XAS characterization and data analysis. Z.L. and P.Q. conducted the in situ XAS experiments. Z.L., L.Z., X.L., L.L., W.Z., Z.W., Y.G., Y.T., S.B., J.W., Z.H., Z.S. and L.W. carried out the TEM, SEM, XPS, XRD and ICP-MS characterization and data analysis. S.L., Z.-Y.W., Y.G., Z.H. and Z.S. performed some supporting experiments. Z.L., P.Q., B.H., Y.Z. and H.Z. analysed and discussed all experimental results and drafted the manuscript. All authors checked the manuscript and agreed with its content.

Corresponding authors

Correspondence to Panzhe Qiao, Bolong Huang, Ye Zhu or Hua Zhang.

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Nature Materials thanks Xiaoguang Duan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Structural characterization of 2H/fcc-Au@2H/fcc-HEA core-shell NSs, fcc/2H/fcc-Au@fcc/2H/fcc-HEA core-shell NRs, 4H/fcc-Au@4H/fcc-HEA core-shell NRs and fcc-Au@fcc-HEA core-shell NWs.

a-e, top: STEM images and STEM-EDS elemental maps (scale bar, 500 nm), bottom left: the corresponding FFT patterns and bottom right: the magnified HAADF-STEM images (scale bar, 1 nm) of the representative 2H/fcc-Au@2H/fcc-IrPtNiFeCoRh (a), 2H/fcc-Au@2H/fcc-IrPtNiFeCoRhPd (b), 2H/fcc-Au@2H/fcc-IrPtNiFeCoRhPdRu (c), 2H/fcc-Au@2H/fcc-IrPtNiFeCoRhPdRuCu (d) and 2H/fcc-Au@2H/fcc-IrPtNiFeCoRhPdRuCuMn (e) NSs, showing 2H/fcc heterophases. f-j, top: STEM images and STEM-EDS elemental maps (scale bar, 10 nm), bottom left: the corresponding FFT patterns and bottom right: the magnified HAADF-STEM images (scale bar, 2 nm) of the representative fcc/2H/fcc-Au@fcc/2H/fcc-IrPtNiFeCoRh (f), fcc/2H/fcc-Au@fcc/2H/fcc-IrPtNiFeCoRhPd (g), fcc/2H/fcc-Au@fcc/2H/fcc-IrPtNiFeCoRhPdRu (h), fcc/2H/fcc-Au@fcc/2H/fcc-IrPtNiFeCoRhPdRuCu (i) and fcc/2H/fcc-Au@fcc/2H/fcc-IrPtNiFeCoRhPdRuCuMn (j) NRs, showing the fcc/2H/fcc heterophases. k-o, top: STEM images and STEM-EDS elemental maps (scale bar, 20 nm), bottom left: the corresponding FFT patterns and bottom right: the magnified HAADF-STEM images (scale bar, 1 nm) of the representative 4H/fcc-Au@4H/fcc-IrPtNiFeCoRh (k), 4H/fcc-Au@4H/fcc-IrPtNiFeCoRhPd (l), 4H/fcc-Au@4H/fcc-IrPtNiFeCoRhPdRu (m), 4H/fcc-Au@4H/fcc-IrPtNiFeCoRhPdRuCu (n) and 4H/fcc-Au@4H/fcc-IrPtNiFeCoRhPdRuCuMn (o) NRs, showing the 4H/fcc heterophases. p-t, top: STEM images and STEM-EDS elemental maps (scale bar, 10 nm), bottom left: the corresponding FFT patterns and bottom right: the magnified HAADF-STEM images (scale bar, 2 nm) of the representative fcc-Au@fcc-IrPtNiFeCoRh (p), fcc-Au@fcc-IrPtNiFeCoRhPd (q), fcc-Au@fcc-IrPtNiFeCoRhPdRu (r), fcc-Au@fcc-IrPtNiFeCoRhPdRuCu (s) and fcc-Au@fcc-IrPtNiFeCoRhPdRuCuMn (t) NWs, showing the pure fcc phase.

Extended Data Fig. 2 Investigation of the formation process of the 4H-IrPtNiFeCo HEA on 4H-Au NW.

a-d, top left: HAADF-STEM images, middle: the magnified atomic-resolution HAADF-STEM images recorded from the blue dashed areas in a-d, respectively, top right: the atomic ratios of different elements in the 4H-Au@4H-IrPtNiFeCo HEA NWs obtained by SEM-EDS, and bottom, the corresponding schematic models at the reaction time of 1 min (a), 5 min (b), 20 min (c) and 60 min (d), respectively.

Extended Data Fig. 3 Characterization of stability of the 4H-IrPtNiFeCo HEA on 4H-Au NW.

a-f, left: In situ HAADF-STEM images, top right: the atomic-resolution HAADF-STEM images recorded from the blue dashed areas in a-f, respectively, and bottom right: the corresponding FFT patterns of the 4H-Au@4H-IrPtNiFeCo NW heated at 500 (a), 600 (b), 700 (c), 800 (d), 900 (e) and 1000 °C (f), respectively. The yellow dashed curves in e and f indicate the phase boundaries.

Extended Data Fig. 4 Phase-dependent electrocatalytic mechanisms of HEA catalysts investigated by DFT calculations.

a,b, The side views of lattice structures and 3D contour plots of the bonding and anti-bonding orbitals near the EF of the 4H-IrPtNiFeCo (a) and fcc-IrPtNiFeCo (b) HEAs. Top panels: relaxed lattice structures. Bottom panels: electronic distributions. The light blue and pink isosurfaces indicate the bonding orbitals and anti-bonding orbitals, respectively. The red, orange, green, blue and pink balls represent Ir, Pt, Ni, Fe and Co atoms, respectively. c,d, Comparisons of the estimated coordination number (c) and the work function and overall d-band center (d) of the 4H- and fcc-IrPtNiFeCo HEAs. e,f, Comparisons of the PDOS of 5 d orbitals of Ir and Pt (e) and 3 d orbitals of Ni, Fe and Co (f) in the 4H- and fcc-IrPtNiFeCo HEAs. g,h, Comparisons of the d-band center (g) and the chemical potential (h) of different elements in the 4H- and fcc-IrPtNiFeCo HEAs. i,j, Comparisons of the calculated reaction energy changes of HER (i) and OER under 1.23 V (j) of the 4H- and fcc-IrPtNiFeCo HEAs.

Extended Data Fig. 5 In situ characterization of coordination environments of 4H-Au@4H-IrPtNiFeCo during the HER and OER.

a-e, Fourier transformed in situ EXAFS spectra in R space for Ir L3-edge (a), Pt L3-edge (b), Ni K-edge (c), Fe K-edge (d) and Co K-edge (e) of 4H-Au@4H-IrPtNiFeCo NWs at −0.15 V, −0.05 V, OCP, 1.25 V and 1.45 V in N2-saturated 0.5 M H2SO4 electrolyte. Note: M represents metal.

Extended Data Fig. 6 Structural evolutions of 4H-Au@4H-IrPtNiFeCo catalyst after the acidic HER and OER.

Schematic illustrations and the corresponding STEM images of the structural evolutions of 4H-Au@4H-IrPtNiFeCo catalyst under acidic HER and OER conditions at 100 and 1,000 mA cm−2 in a PEMWE.

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Supplementary Figs. 1–72, Notes 1–15 and Tables 1–6.

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Li, Z., Zhang, A., Chen, C. et al. Synthesis of 4H-phase high-entropy alloys for electrocatalysis. Nat. Mater. (2026). https://doi.org/10.1038/s41563-026-02562-1

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