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Synthesis of noble/non-noble metal alloy nanostructures via an active-hydrogen-involved interfacial reduction strategy

Nature Synthesis volume 2, pages 119–128 (2023)Cite this article

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Abstract

Traditional solution-phase synthesis of noble/non-noble metal alloy nanocrystals lacks control over metal co-reduction due to the difference in reduction potentials. As a result, these synthetic routes lead to constrained compositional space. To address this problem, we have developed an active-hydrogen (H*)-involved interfacial reduction method for the synthesis of alloy nanostructures. The introduction of HNO2 into the reaction generates H* at the metal seed/solution interface, creating a highly reducing environment. Metal reduction, therefore, migrates from the solution phase to the interface, and H*, as a strong reducing agent, can negate the effect of the reduction potential differences of metal salts, leading to their effective co-reduction. We demonstrate the synthesis of a library of Pt–M alloy nanoshells (M = Fe, Co, Ni, Ga, In, Sn, Pb, Bi) on palladium octahedral cores with precise compositional control, enabling screening of the materials as catalysts for the hydrogen evolution reaction. This strategy paves a way for noble/non-noble metal alloy nanostructures with superior synthetic control for a broad range of applications.

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Fig. 1: Interfacial synthesis of Pt–Ni alloy nanoshells on octahedral Pd nanocrystals.
Fig. 2: Cs-corrected high-resolution electron microscopy characterizations of the octahedral Pd@Pt–Ni alloy core–shell nanocrystals.
Fig. 3: The active H*-involved interfacial reduction mechanism for the precise synthesis of Pt–Ni alloy nanoshells.
Fig. 4: Library synthesis of octahedral Pd@Pt–M alloy core–shell nanocrystals.
Fig. 5: Electrochemical performance of the octahedral Pd@Pt–Ni alloy core–shell nanocrystals in the alkaline HER.

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All data supporting the findings of this study are available in the main text or Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (22071191), the Key Research and Development Projects of Shaanxi Province (2021GXLH-Z-022), the Key Scientific and Technological Innovation Team of Shaanxi Province (2020TD-001) and the Fundamental Research Funds for the Central Universities. We thank ShanghaiTech University and the Center for High-resolution Electron Microscopy (CћEM) through EM-19430216 for support with the spherical-aberration-corrected HR-STEM analysis and the Instrument Analysis Center of Xi’an Jiaotong University for assistance with the ICP-MS measurements. We thank S. Shen and R. Wang at Xi’an Jiaotong University for their help with the EPR.

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Authors and Affiliations

  1. State Key Laboratory of Multiphase Flow in Power Engineering, Frontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an, China

    Zhaojun Liu, Zhixue Zhang, Xiaoxiao Wang, Kai Liu, Zhun Qiao, Moxuan Liu, Shumeng Zhang, Zerui Mu & Chuanbo Gao

  2. Center for High-resolution Electron Microscopy (CħEM), School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

    Yilan Jiang & Qing Zhang

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  1. Zhaojun Liu
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Contributions

C.G. conceived the idea and supervised the project. Z.L. performed the synthesis, characterization and electrocatalysis. Y.J. and Q.Z. conducted atomic-resolution electron microscopy of the materials. Z.Z., X.W., K.L., Z.Q., M.L., S.Z. and Z.M. assisted with the materials synthesis and characterizations. Z.L. and C.G. wrote the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Chuanbo Gao.

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Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–26 and Tables 1–4.

Source data

Source Data Fig. 3

Mass spectra and GC spectra of gaseous products from the synthesis; the Ni/Pt ratios in the alloy nanocrystals, plotted against the concentration of NaNO2 and the Ni/Pt ratios in the synthesis precursors.

Source Data Fig. 5

Electrochemical performance data.

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Liu, Z., Jiang, Y., Zhang, Z. et al. Synthesis of noble/non-noble metal alloy nanostructures via an active-hydrogen-involved interfacial reduction strategy. Nat. Synth 2, 119–128 (2023). https://doi.org/10.1038/s44160-022-00217-y

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