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Multistep nucleation of nanocrystals in aqueous solution

Nature Chemistry volume 9, pages 77–82 (2017)Cite this article

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Abstract

The nucleation and growth of solids from solutions impacts many natural processes and is fundamental to applications in materials engineering and medicine. For a crystalline solid, the nucleus is a nanoscale cluster of ordered atoms that forms through mechanisms still poorly understood. In particular, it is unclear whether a nucleus forms spontaneously from solution via a single- or multiple-step process. Here, using in situ electron microscopy, we show how gold and silver nanocrystals nucleate from supersaturated aqueous solutions in three distinct steps: spinodal decomposition into solute-rich and solute-poor liquid phases, nucleation of amorphous nanoclusters within the metal-rich liquid phase, followed by crystallization of these amorphous clusters. Our ab initio calculations on gold nucleation suggest that these steps might be associated with strong gold–gold atom coupling and water-mediated metastable gold complexes. The understanding of intermediate steps in nuclei formation has important implications for the formation and growth of both crystalline and amorphous materials.

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Figure 1: Proposed three-step pathway for gold and silver nucleation in solution.
Figure 2: Amorphous gold nanoclusters appear from gold-rich spinodal structures.
Figure 3: Crystallinities of 74 gold nanoclusters that emerged from gold-rich phases.
Figure 4: Calculations of ground-state energies for a hydrated pair of gold atoms.

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Acknowledgements

This work was supported by the Singapore National Research Foundation's Competitive Research Program funding (NRF-CRP9-2011-04) and the Young Investigator Award (NUSYIA-FY14-P17) from the National University of Singapore. C.A.N. and M.B. acknowledge support from grant No. NRF-CRP8-2011-07, U.M. and P.M. acknowledges support from the Microbiology Institute (Singapore) and the Centre for Bioimaging Sciences. N.D.L. thanks the support of the Lee Kuan Yew Endowment Fund, and National University of Singapore internal grant No. 154-000-606-112. The work of P.K. was supported by the National Science Foundation Division of Materials Research Grant No. 1309765 and by the American Chemical Society Petroleum Research Funding Grant No. 53062-ND6.

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Authors and Affiliations

  1. Department of Physics, National University of Singapore, 2 Science Drive 3, 117551, Singapore

    N. Duane Loh, Jun Zhong & Utkur Mirsaidov

  2. Department of Biological Sciences, Centre for Bioimaging Sciences, National University of Singapore, 14 Science Drive 4, 117543, Singapore

    N. Duane Loh, Jun Zhong, Paul Matsudaira & Utkur Mirsaidov

  3. Department of Chemistry, University of Illinois at Chicago, Chicago, 60607, Illinois, USA

    Soumyo Sen & Petr Král

  4. Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, 138634, Singapore

    Michel Bosman

  5. Department of Materials Science and Engineering, National University of Singapore, 9 Engineering Drive 1, 117575, Singapore

    Michel Bosman

  6. Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore

    Shu Fen Tan & Christian A. Nijhuis

  7. Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, 6 Science Drive 2, 117546, Singapore

    Christian A. Nijhuis & Utkur Mirsaidov

  8. Department of Physics and Biopharmaceutical Sciences, University of Illinois at Chicago, Chicago, 60607, Illinois, USA

    Petr Král

  9. MechanoBiology Institute, National University of Singapore, 5A Engineering Drive 1, 117576, Singapore

    Paul Matsudaira

  10. NanoCore, National University of Singapore, 4 Engineering Drive 3, 117576, Singapore

    Utkur Mirsaidov

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  1. N. Duane Loh
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Contributions

U.M. and P.M. conceived the study. U.M. designed the in situ experiments, which he performed together with M.B. and S.F.T.; N.D.L. designed and implemented the image processing and statistical analysis on the TEM images, with help from J.Z. and input from U.M., P.M., C.A.N. and M.B.; N.D.L. did and, with U.M. and M.B., wrote up the analyses in the Supplementary Information on CNT, spinodal decomposition and the effects of the electron beam. S.S. and P.K. carried out the hybrid molecular dynamics calculations. N.D.L., C.A.N., P.K., P.M. and U.M. wrote the manuscript from discussions that arose from all authors.

Corresponding authors

Correspondence to Christian A. Nijhuis, Petr Král or Utkur Mirsaidov.

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The authors declare no competing financial interests.

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Loh, N., Sen, S., Bosman, M. et al. Multistep nucleation of nanocrystals in aqueous solution. Nature Chem 9, 77–82 (2017). https://doi.org/10.1038/nchem.2618

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