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.

  • Letter
  • Published:

Three-dimensional atomic-scale structure of size-selected gold nanoclusters

Nature volume 451, pages 46–48 (2008)Cite this article

Abstract

An unambiguous determination of the three-dimensional structure of nanoparticles is challenging1. Electron tomography requires a series of images taken for many different specimen orientations2. This approach is ideal for stable and stationary structures3. But ultrasmall nanoparticles are intrinsically structurally unstable and may interact with the incident electron beam4,5,6, constraining the electron beam density that can be used and the duration of the observation. Here we use aberration-corrected scanning transmission electron microscopy7, coupled with simple imaging simulation, to determine with atomic resolution the size, three-dimensional shape, orientation and atomic arrangement of size-selected gold nanoclusters that are preformed in the gas phase and soft-landed on an amorphous carbon substrate. The structures of gold nanoclusters containing 309±6 atoms can be identified with either Ino-decahedral, cuboctahedral or icosahedral geometries. Comparison with theoretical modelling of the system suggests that the structures are consistent with energetic considerations. The discovery that nanoscale gold particles function as active and selective catalysts for a variety of important chemical reactions has provoked much research interest in recent years8,9,10,11,12. We believe that the detailed structure information we provide will help to unravel the role of these nanoclusters in size- and structure-specific catalytic reactions11,12. We note that the technique will be of use in investigations of other supported ultrasmall metal cluster systems.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: High-resolution HAADF-STEM images of Au 309 clusters on a carbon film.
Figure 2: Relationship between integrated HAADF intensity and size of gold clusters.
Figure 3: Three-dimensional atomic structure of a gold cluster ( N = 309 ± 6).

Similar content being viewed by others

References

  1. Koga, K., Ikeshoji, T. & Sugawara, K. Size- and temperature-dependent structural transitions in gold nanoparticles. Phys. Rev. Lett. 92, 115504–115507 (2004)

    Article  ADS  Google Scholar 

  2. Midgley, P. A. & Weyland, M. 3D electron microscopy in the physical sciences: the development of Z-contrast and EFTEM tomography. Ultramicroscopy 96, 413–431 (2003)

    Article  CAS  Google Scholar 

  3. Arslan, I., Yates, T. J. V., Browning, N. D. & Midgley, P. A. Embedded nanostructures revealed in three dimensions. Science 309, 2195–2198 (2005)

    Article  ADS  CAS  Google Scholar 

  4. Iijima, S. & Ichihashi, T. Structural instability of ultrafine particles of metals. Phys. Rev. Lett. 56, 616–619 (1986)

    Article  ADS  CAS  Google Scholar 

  5. Ajayan, P. M. & Marks, L. D. Experimental evidence for quasimelting in small particles. Phys. Rev. Lett. 63, 279–282 (1989)

    Article  ADS  CAS  Google Scholar 

  6. Marks, L. D. Experimental studies of small particles structures. Rep. Prog. Phys. 57, 603–649 (1994)

    Article  ADS  CAS  Google Scholar 

  7. Batson, P. E., Dellby, N. & Krivanek, O. L. Sub-angstrom resolution using aberration corrected electron optics. Nature 418, 617–620 (2002)

    Article  ADS  CAS  Google Scholar 

  8. Haruta, M. Size- and support-dependency in the catalysis of gold. Catal. Today 36, 153–166 (1997)

    Article  CAS  Google Scholar 

  9. Sanchez, A. et al. When gold is not noble: nanoscale gold catalysts. J. Phys. Chem. A 103, 9573–9578 (1999)

    Article  CAS  Google Scholar 

  10. Hughes, M. D. et al. Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions. Nature 437, 1132–1135 (2005)

    Article  ADS  CAS  Google Scholar 

  11. Tsunoyama, H., Sakurai, H., Negishi, Y. & Tsukuda, T. Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water. J. Am. Chem. Soc. 127, 9374–9375 (2005)

    Article  CAS  Google Scholar 

  12. Chen, M. S. & Goodman, D. W. Structure-activity relationships in supported Au catalysts. Catal. Today 111, 22–33 (2006)

    Article  CAS  Google Scholar 

  13. Li, Z. Y., Yuan, J., Chen, Y., Palmer, R. E. & Wilcoxon, J. P. Direct imaging of core-shell structure in silver-gold bimetallic nanoparticles. Appl. Phys. Lett. 87, 243103 (2005)

    Article  ADS  Google Scholar 

  14. Li, Z. Y., Yuan, J., Chen, Y., Palmer, R. E. & Wilcoxon, J. P. Local three-dimensional visualization of nanoparticle assemblies. Adv. Mater. 17, 2885–2888 (2005)

    Article  CAS  Google Scholar 

  15. Krivanek, O. L., Delby, N. & Lupini, A. R. Towards sub-angstrom electron beams. Ultramicroscopy 78, 1–11 (1999)

    Article  CAS  Google Scholar 

  16. Kirkland, E. J. Advanced Computing in Electron Microscopy (Plenum Press, New York/London, 1998)

    Book  Google Scholar 

  17. Smith, D. J., Petford-Long, A. K., Wallenberg, L. R. & Bovin, J.-O. Dynamic atomic-level rearrangements in small gold particles. Science 233, 872–875 (1986)

    Article  ADS  CAS  Google Scholar 

  18. Bovin, J.-O., Wallenberg, R. & Smith, D. J. Imaging of atomic clouds outside the surfaces of gold crystals by electron microscopy. Nature 317, 47–49 (1985)

    Article  ADS  CAS  Google Scholar 

  19. Schebarchov, D. & Hendy, S. C. Transition from icosahedral to decahedral structure in a coexisting solid-liquid nickel cluster. Phys. Rev. Lett. 95, 116101–116104 (2005)

    Article  ADS  CAS  Google Scholar 

  20. Hansen, P. L. et al. Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science 295, 2053–2055 (2003)

    Article  ADS  Google Scholar 

  21. Pratontep, S., Carroll, S. J., Xirouchaki, C., Streun, M. & Palmer, R. E. Size-selected cluster beam source based on radio frequency magnetron plasma sputtering and gas condensation. Rev. Sci. Instrum. 76, 045103–045109 (2005)

    Article  ADS  Google Scholar 

  22. von Issendorff, B. & Palmer, R. E. A new high transmission infinite range mass selector for cluster and nanoparticle beams. Rev. Sci. Instrum. 70, 4497–4501 (1999)

    Article  ADS  CAS  Google Scholar 

  23. Palmer, R. E., Pratontep, S. & Boyen, H.-G. Nanostructured surfaces from size-selected clusters. Nature Mater. 2, 443–448 (2003)

    Article  ADS  CAS  Google Scholar 

  24. Bleloch, A. L. & Lupini, A. Imaging at the picoscale. Mater. Today 7, 42–48 (2004)

    Article  CAS  Google Scholar 

  25. Jiang, J., Yuan, J. & Bleloch, A. L. Cluster-scale composition determination in a boron-rich compound. Appl. Phys. Lett. 91, 113107 (2007)

    Article  ADS  Google Scholar 

  26. Cleri, F. & Rosato, V. Tight-binding potentials for transition metals and alloys. Phys. Rev. B 48, 22–33 (1993)

    Article  ADS  CAS  Google Scholar 

  27. Johnston, R. L. Evolving better nanoparticles: Genetic algorithms for optimising cluster geometries. Dalton Trans. 4193–4207 (2003)

Download references

Acknowledgements

We thank Y. Chen for assistance with the electron microscopy work in Birmingham. We gratefully acknowledge the UK Engineering and Physical Science Research Council (EPSRC) and the EU for their financial support of the cluster work. The EPSRC funded the UK SuperSTEM facility at Daresbury Laboratory. N.P.Y. and B.C.C. acknowledge the EPSRC and the University of Birmingham for PhD funding, respectively. The work at Tsinghua University was supported by the Ministry of Science and Technology and Ministry of Education in China.

Author information

Authors and Affiliations

  1. Nanoscale Physics Research Laboratory, School of Physics and Astronomy,,

    Z. Y. Li, N. P. Young, M. Di Vece, S. Palomba & R. E. Palmer

  2. School of Chemistry, University of Birmingham, Birmingham B15 2TT, UK ,

    B. C. Curley & R. L. Johnston

  3. UK SuperSTEM Laboratory, Daresbury Laboratory, Daresbury WA4 4AD, UK

    A. L. Bleloch

  4. Beijing Electron Microscopy Centre,

    J. Jiang & J. Yuan

  5. Laboratory of Advanced Materials and Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

    J. Jiang & J. Yuan

Authors
  1. Z. Y. Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. N. P. Young
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Di Vece
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Palomba
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. R. E. Palmer
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. L. Bleloch
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. B. C. Curley
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. R. L. Johnston
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. J. Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. J. Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Z. Y. Li.

Supplementary information

Supplementary Information

The file contains Supplementary Notes and Figures. (PDF 143 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Li, Z., Young, N., Di Vece, M. et al. Three-dimensional atomic-scale structure of size-selected gold nanoclusters. Nature 451, 46–48 (2008). https://doi.org/10.1038/nature06470

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature06470

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced 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