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Retrosynthetic design of core–shell nanoparticles for thermal conversion to monodisperse high-entropy alloy nanoparticles

Nature Synthesis volume 3, pages 175–184 (2024)Cite this article

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Abstract

High-entropy alloys (HEAs) consisting of five or more elements have gained considerable attention due to their distinctive properties. However, synthesizing monodisperse HEA nanoparticles (NPs) is challenging through colloidal chemistry due to differences in the reduction rates of metal precursors and poor understanding of reaction intermediates. Here we propose a general approach to HEA NPs through an NP conversion pathway, where two-phase core–shell NPs are predictably synthesized via colloidal chemistry and then converted into single-phase HEA NPs by thermal annealing. This study establishes the necessary synthesis principles for the precursor core–shell NPs by considering the relative redox potentials of metal or metal precursors and the inherent lattice properties of the selected metals. Once monodisperse core–shell NPs were synthesized, they were converted into single-phase HEA NPs (constituent metals studied include Pd, Cu, Pt, Ni, Co, Au, Ag and Sn) by a simple annealing procedure that is suitable for different NP supports. We demonstrate the ability to manipulate the degree of intermixing between the core and shell phases and the generality of this NP conversion strategy to monodisperse HEA NPs.

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Fig. 1: Illustration of the nanoparticle (NP) conversion process to synthesize high entropy alloy (HEA) NPs.
Fig. 2: Characterization of Au-containing NPs.
Fig. 3: Characterization of NPs from redox potential (Ered) reactivity study.
Fig. 4: Characterization of Sn-containing NPs.
Fig. 5: Morphological and compositional characterization of monodisperse HEA NPs.

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The data that substantiate the study’s findings and contribute to the assessment of the paper’s conclusions can be accessed within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

S.E.S., N.K., M.M., I.H.S., J.W. and S.L.A.B. acknowledge financial support from Indiana University and the US National Science Foundation (NSF CHE 2203349 received by S.E.S.). The authors acknowledge support from Indiana University’s Electron Microscopy Center, XPS facility (access to XPS at the Nanoscale Characterization Facility was provided by the NSF Award DMR MRI-1126394 received by S.E.S.), and Nanoscale Characterization Facility for access to instrumentation. They also thank X. Zhan, E. Verma and Y. Losovyj for their helpful discussions.

Author information

Authors and Affiliations

  1. Department of Chemistry, Indiana University, Bloomington, Bloomington, IN, USA

    Nabojit Kar, Maximilian McCoy, Joshua Wolfe, Sandra L. A. Bueno, Ibrahim H. Shafei & Sara E. Skrabalak

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  1. Nabojit Kar
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  2. Maximilian McCoy
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Contributions

N.K. and S.E.S. were responsible for the project concept and design of experiments. N.K. developed the synthesis of bimetallic and core–shell NPs and characterizations. M.M. and J.W. helped in synthesis of AuCu and Pd3Sn core–shell NP synthesis, respectively. I.H.S. contributed in temperature-dependent experiments. S.L.A.B. contributed some STEM–EDS characterization as well as some control experiments. This manuscript was written through the contributions of all authors. All authors have given approval to the final version of this manuscript.

Corresponding author

Correspondence to Sara E. Skrabalak.

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Nature Synthesis thanks Zhiming Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–43, discussion, Table 1, Notes 1 and 2, and references.

Source data

Source Data Fig. 2

Unprocessed data of STEM–EDS linescan and SEM–EDS spectra.

Source Data Fig. 3

Unprocessed data of STEM–EDS linescan and SEM–EDS spectra.

Source Data Fig. 4

Unprocessed data of STEM–EDS linescan and SEM–EDS spectra.

Source Data Fig. 5

Unprocessed data of STEM–EDS linescan, XRD pattern and individual XPS spectra.

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Kar, N., McCoy, M., Wolfe, J. et al. Retrosynthetic design of core–shell nanoparticles for thermal conversion to monodisperse high-entropy alloy nanoparticles. Nat. Synth 3, 175–184 (2024). https://doi.org/10.1038/s44160-023-00409-0

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