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A selenium-mediated layer-by-layer synthetic strategy for multilayered multicomponent nanocrystals

Nature Synthesis volume 3, pages 1299–1309 (2024)Cite this article

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Abstract

Ordered heterostructured nanocrystals with large compositional and morphological diversity are important for many applications. However, design of multicomponent nanostructures at the atomic level is difficult due to the elusive nucleation and growth processes in a solution-phase environment. Here we report a modular synthetic protocol that produces ordered multilayered nanostructures with small particle size by layer-by-layer growth. We introduce a selenium capping agent to hinder self-assembly, aggregation and phase segregation of nanostructures, while also sequencing the priority of metal atoms that migrate in the substrate lattice according to different metal–selenium bonding strengths, leading to a layer-by-layer growth for ordered nanostructures. The multilayered multicomponent nanocrystals are demonstrated in an alkaline polymer electrolyte fuel cell by using PtRuZn-SKE (SKE, selenium-mediated Kirkendall effect) as the anodic hydrogen oxidation reaction catalyst, which can deliver a high peak power density of 1.52 W cm−2 in H2–O2 and 1.12 W cm−2 in H2–air (CO2-free) while operating at 600 mA cm−2 for 100 h. This generalizable strategy provides a predictable synthetic pathway to complex nanocrystals.

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Fig. 1: Overview of the controllable synthesis of platinum-based NCs with multilayer heterostructures.
Fig. 2: Synthesis and structural analyses of binary PtRu-SKE NCs.
Fig. 3: Analysis of multilayered platinum-based NC growth processes.
Fig. 4: DFT calculations for the mechanism of layer-by-layer formation.
Fig. 5: Electrocatalytic alkaline HOR measurements and full-cell performance.

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Data availability

Additional characterization data, experimental data, and theoretical calculation data are provided in the Supplementary Information. Source data are provided with this paper.

Code availability

The computational codes used in this work are available within the commercial VASP and the Gaussian 09 packages.

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Acknowledgements

X.H. acknowledges support from the National Key R&D Program of China (2020YFB1505802), the Ministry of Science and Technology (2017YFA0208200), the National Natural Science Foundation of China (22025108, U21A20327, 22121001) and start-up fundings from Xiamen University. J.H. acknowledges support from the National Natural Science Foundation of China (52272256). C.H. acknowledges support from the Postdoctoral Science Foundation of China (2021M702731). J.X. acknowledges the grants from the Research Grants Council of the Hong Kong Special Administrative Region, China (grant number 21301324).

Author information

Author notes

  1. These authors contributed equally: Chun Hu, Yangyang Zhang, Renjie Ren.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Chun Hu, Yuanzhi Tan & Xiaoqing Huang

  2. State Key Laboratory of Reliability and Intelligence of Electrical Equipment, School of Materials Science and Engineering, Hebei University of Technology, Tianjin, China

    Yangyang Zhang & Shijian Zheng

  3. College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan, China

    Renjie Ren & Lin Zhuang

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

    Jijian Xu

  5. Department of Chemistry, Western University, London, Ontario, Canada

    Lijia Liu

  6. Synchrotron Soleil, L’Orme des Mersiers, St-Aubin, France

    Qingyu Kong

  7. Max Planck Institute for Chemical Physics of Solids, Dresden, Germany

    Zhiwei Hu

  8. Materials Genome Institute, Shanghai University, Shanghai, China

    Jian Huang

  9. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, China

    Xiaoqing Huang

Authors
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Contributions

X.H. supervised the project. C.H. carried out the materials synthesis, electrochemical experiments, electron microscopy experiments, data processing and analysis, and manuscript writing. J.H. performed the DFT calculations. J.X. revised the manuscript. Y.T. Y.T. contacted the spherical aberration transmission electron microscopy testing cooperation. Y.Z. and S.Z. performed the spherical aberration transmission electron microscopy experiments. R.R. and L.Z. conducted the membrane electrode assembly measurements. Q.K. and Z.H. performed the XAS measurements. L.L. analysed the XAS data. All authors discussed and commented on the manuscript.

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Correspondence to Jijian Xu, Jian Huang, Yuanzhi Tan or Xiaoqing Huang.

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Nature Synthesis thanks Hao Jing, J. R. Sambrano and the other, anonymous, reviewer(s) 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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Hu, C., Zhang, Y., Ren, R. et al. A selenium-mediated layer-by-layer synthetic strategy for multilayered multicomponent nanocrystals. Nat. Synth 3, 1299–1309 (2024). https://doi.org/10.1038/s44160-024-00598-2

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