Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Multistep nucleation of nanocrystals in aqueous solution

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.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

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.

References

  1. Sear, R. P. The non-classical nucleation of crystals: microscopic mechanisms and applications to molecular crystals, ice and calcium carbonate. Int. Mater. Rev. 57, 328–356 (2012).

    Article  CAS  Google Scholar 

  2. De Yoreo, J. J. & Vekilov, P. G. in Biomineralization (eds Dove, P., De Yoreo, J. & Weiner, S.) 57–93 (Mineralogical Society of America, 2003).

    Book  Google Scholar 

  3. Vekilov, P. G. Dense liquid precursor for the nucleation of ordered solid phases from solution. Cryst. Growth Des. 4, 671–685 (2004).

    Article  CAS  Google Scholar 

  4. Kalikmanov, V. I. Nucleation Theory (Lecture Notes in Physics Vol. 860, Springer, 2013).

    Book  Google Scholar 

  5. De Yoreo, J. J. et al. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 349, aaa6760 (2015).

    Article  Google Scholar 

  6. Hill, P. G. Condensation of water vapour during supersonic expansion in nozzles. J. Fluid Mech. 25, 593–620 (1966).

    Article  Google Scholar 

  7. Vekilov, P. G. The two-step mechanism of nucleation of crystals in solution. Nanoscale 2, 2346–2357 (2010).

    Article  CAS  Google Scholar 

  8. Sanz, E. et al. Homogeneous ice nucleation at moderate supercooling from molecular simulation. J. Am. Chem. Soc. 135, 15008–15017 (2013).

    Article  CAS  Google Scholar 

  9. De Yoreo, J. Crystal nucleation: more than one pathway. Nat. Mater. 12, 284–285 (2013).

    Article  CAS  Google Scholar 

  10. Erdemir, D., Lee, A. Y. & Myerson, A. S. Nucleation of crystals from solution: classical and two-step models. Acc. Chem. Res. 42, 621–629 (2009).

    Article  CAS  Google Scholar 

  11. Cahn, J. W. & Hilliard, J. E. Free energy of a nonuniform system. III. Nucleation in a two-component incompressible fluid. J. Chem. Phys. 31, 688–699 (1959).

    Article  CAS  Google Scholar 

  12. Wallace, A. F. et al. Microscopic evidence for liquid–liquid separation in supersaturated CaCO3 solutions. Science 341, 885–889 (2013).

    Article  CAS  Google Scholar 

  13. Nielsen, M. H., Aloni, S. & De Yoreo, J. J. In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways. Science 345, 1158–1162 (2014).

    Article  CAS  Google Scholar 

  14. Vekilov, P. G. Phase diagrams and kinetics of phase transitions in protein solutions. J. Phys. Condens. Matter 24, 193101 (2012).

    Article  Google Scholar 

  15. Zheng, H. et al. Observation of single colloidal platinum nanocrystal growth trajectories. Science 324, 1309–1312 (2009).

    Article  CAS  Google Scholar 

  16. Woehl, T. J., Evans, J. E., Arslan, I., Ristenpart, W. D. & Browning, N. D. Direct in situ determination of the mechanisms controlling nanoparticle nucleation and growth. ACS Nano 6, 8599–8610 (2012).

    Article  CAS  Google Scholar 

  17. Patterson, J. P. et al. Observing the growth of metal–organic frameworks by in situ liquid cell transmission electron microscopy. J. Am. Chem. Soc. 137, 7322–7328 (2015).

    Article  CAS  Google Scholar 

  18. Tromp, R. M. & Ross, F. M. Advances in in situ ultra-high vacuum electron microscopy growth of SiGe on Si. Annu. Rev. Mater. Sci. 30, 431–449 (2000).

    Article  CAS  Google Scholar 

  19. Privman, V., Goia, D. V., Park, J. & Matijevic, E. Mechanism of formation of monodispersed colloids by aggregation of nanosize precursors. J. Colloid Interface Sci. 213, 36–45 (1999).

    Article  CAS  Google Scholar 

  20. Mikhlin, Y. et al. Submicrometer intermediates in the citrate synthesis of gold nanoparticles: new insights into the nucleation and crystal growth mechanisms. J. Colloid Interface Sci. 362, 330–336 (2011).

    Article  CAS  Google Scholar 

  21. Sambles, J. R. An electron microscope study of evaporating gold particles: the Kelvin equation for liquid gold and the lowering of the melting point of solid gold particles. Proc. R. Soc. Lond. A. 324, 339–351 (1971).

    Article  CAS  Google Scholar 

  22. Chushak, Y. G. & Bartell, L. S. Melting and freezing of gold nanoclusters. J. Phys. Chem. B 105, 11605–11614 (2001).

    Article  CAS  Google Scholar 

  23. Gachard, E. et al. Radiation-induced and chemical formation of gold clusters. New J. Chem. 22, 1257–1265 (1998).

    Article  CAS  Google Scholar 

  24. Xin, H. L. & Zheng, H. In situ observation of oscillatory growth of bismuth nanoparticles. Nano Lett. 12, 1470–1474 (2012).

    Article  CAS  Google Scholar 

  25. Aabdin, Z. et al. Bonding pathways of gold nanocrystals in solution. Nano Lett. 14, 6639–6643 (2014).

    Article  CAS  Google Scholar 

  26. Lu, J., Aabdin, Z., Loh, N. D., Bhattacharya, D. & Mirsaidov, U. Nanoparticle dynamics in a nanodroplet. Nano Lett. 14, 2111–2115 (2014).

    Article  CAS  Google Scholar 

  27. Park, J. et al. 3D structure of individual nanocrystals in solution by electron microscopy. Science 349, 290–295 (2015).

    Article  CAS  Google Scholar 

  28. Seidell, A. & Linke, W. F. Solubilities of Inorganic and Metal–Organic Compounds (Van Nostrand, 1958).

    Google Scholar 

  29. Laughlin, D. E. & Soffa, W. Spinodal structures. ASM Handbook 9, 652–654 (1985).

    Google Scholar 

  30. Dey, G. R., El Omar, A. K., Jacob, J. A., Mostafavi, M. & Belloni, J. Mechanism of trivalent gold reduction and reactivity of transient divalent and monovalent gold ions studied by gamma and pulse radiolysis. J. Phys. Chem. A 115, 383–391 (2011).

    Article  CAS  Google Scholar 

  31. Rappl, T. J. & Balsara, N. P. Does coarsening begin during the initial stages of spinodal decomposition? J. Chem. Phys. 122, 22–25 (2005).

    Article  Google Scholar 

  32. Guenther, G. & Guillon, O. Models of size-dependent nanoparticle melting tested on gold. J. Mater. Sci. 49, 7915–7932 (2014).

    Article  CAS  Google Scholar 

  33. Gruene, P. et al. Structures of neutral Au7, Au19, and Au20 clusters in the gas phase. Science 321, 674–676 (2008).

    Article  CAS  Google Scholar 

  34. Li, L. et al. Noncrystalline-to-crystalline transformations in Pt nanoparticles. J. Am. Chem. Soc. 135, 13062–13072 (2013).

    Article  CAS  Google Scholar 

  35. Belloni, J. Nucleation, growth and properties of nanoclusters studied by radiation chemistry application to catalysis. Catal. Today 113, 141–156 (2006).

    Article  CAS  Google Scholar 

  36. Williamson, M. J., Tromp, R. M., Vereecken, P. M., Hull, R. & Ross, F. M. Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface. Nat. Mater. 2, 532–536 (2003).

    Article  CAS  Google Scholar 

  37. Ross, F. M. Opportunities and challenges in liquid cell electron microscopy. Science 350, aaa9886 (2015).

    Article  Google Scholar 

  38. Mirsaidov, U. M., Zheng, H., Bhattacharya, D., Casana, Y. & Matsudaira, P. Direct observation of stick-slip movements of water nanodroplets induced by an electron beam. Proc. Natl Acad. Sci. USA 109, 7187–7190 (2012).

    Article  CAS  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

Authors

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.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 4709 kb)

Supplementary information

Supplementary Movie 1 (MOV 4220 kb)

Supplementary information

Supplementary Movie 2 (MOV 13572 kb)

Supplementary information

Supplementary Movie 3 (MOV 6612 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.2618

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing