Abstract
Understanding the mixing behaviour of elements in a multielement material is important to control its structure and property. When the size of a multielement material is decreased to the nanoscale, the miscibility of elements in the nanomaterial often changes from its bulk counterpart. However, there is a lack of comprehensive and quantitative experimental insight into this process. Here we explored how the miscibility of Au and Rh evolves in nanoparticles of sizes varying from 4 to 1 nm and composition changing from 15% Au to 85% Au. We found that the two immiscible elements exhibit a phase-separation-to-alloy transition in nanoparticles with decreased size and become completely miscible in sub-2 nm particles across the entire compositional range. Quantitative electron microscopy analysis and theoretical calculations were used to show that the observed immiscibility-to-miscibility transition is dictated by particle size, composition and possible surface adsorbates present under the synthesis conditions.
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Data availability
The data supporting the findings of this study are available within the Article and its Supplementary Information, and are available from the corresponding author on reasonable request.
Code availability
The source codes of the algorithm for the HAADF-STEM image analysis are available via Zenodo at https://doi.org/10.5281/zenodo.10510952.
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Acknowledgements
This work was supported by Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences & Biosciences Division, US Department of Energy (DOE), under Contract DE-AC02-05CH11231, FWP CH030201 (Catalysis Research Program). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, US DOE, under contract no. DE-AC02-05CH11231. This work made use of the TEM facilities at the Cornell Center for Materials Research (CCMR), which are supported through the National Science Foundation Materials Research Science and Engineering Center (NSF MRSEC) program (DMR-1719875). P.-C.C. acknowledges support from Kavli ENSI Heising-Simons Fellowship. J.J. acknowledges fellowship support from Suzhou Industrial Park. Y.Y. acknowledges support from Miller Fellowship. C.A.M. acknowledges the National Defense Science and Engineering Graduate (NDSEG) fellowship and the Kavli ENSI Graduate Student Fellowship for financial support. This research used resources of the National Energy Research Scientific Computing Center, a US DOE Office of Science User Facility supported by the Office of Science of the US DOE under contract no. DE-AC02-05CH11231 using NERSC award BES-ERCAP0024004.
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P.-C.C. and P.Y. conceived the ideas and designed the experiments. P.-C.C. performed the nanoparticle synthesis and conducted the electron microscopy characterization. M.G. designed the quantitative analysis algorithm. P.-C.C. and M.G. analysed the electron microscopy characterization data and performed the STEM image simulation. C.A.M. and K.A.P. performed the DFT calculations and theoretical analysis. C.S., J.J., Y.Y. and A.L.M. discussed the experimental results. P.-C.C., M.G. and P.Y. wrote the manuscript with editorial input from the other authors. P.Y. supervised the project.
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Chen, PC., Gao, M., McCandler, C.A. et al. Complete miscibility of immiscible elements at the nanometre scale. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01626-0
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DOI: https://doi.org/10.1038/s41565-024-01626-0
