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:

Ultrastable silver nanoparticles

Nature volume 501, pages 399–402 (2013)Cite this article

Subjects

Abstract

Noble-metal nanoparticles have had a substantial impact across a diverse range of fields, including catalysis1, sensing2, photochemistry3, optoelectronics4,5, energy conversion6 and medicine7. Although silver has very desirable physical properties, good relative abundance and low cost, gold nanoparticles have been widely favoured owing to their proved stability and ease of use. Unlike gold, silver is notorious for its susceptibility to oxidation (tarnishing), which has limited the development of important silver-based nanomaterials. Despite two decades of synthetic efforts, silver nanoparticles that are inert or have long-term stability remain unrealized. Here we report a simple synthetic protocol for producing ultrastable silver nanoparticles, yielding a single-sized molecular product in very large quantities with quantitative yield and without the need for size sorting. The stability, purity and yield are substantially better than those for other metal nanoparticles, including gold, owing to an effective stabilization mechanism. The particular size and stoichiometry of the product were found to be insensitive to variations in synthesis parameters. The chemical stability and structural, electronic and optical properties can be understood using first-principles electronic structure theory based on an experimental single-crystal X-ray structure. Although several structures have been determined for protected gold nanoclusters8,9,10,11,12, none has been reported so far for silver nanoparticles. The total structure of a thiolate-protected silver nanocluster reported here uncovers the unique structure of the silver thiolate protecting layer, consisting of Ag2S5 capping structures. The outstanding stability of the nanoparticle is attributed to a closed-shell 18-electron configuration with a large energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, an ultrastable 32-silver-atom excavated-dodecahedral13 core consisting of a hollow 12-silver-atom icosahedron encapsulated by a 20-silver-atom dodecahedron, and the choice of protective coordinating ligands. The straightforward synthesis of large quantities of pure molecular product promises to make this class of materials widely available for further research and technology development14,15,16,17,18.

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: Optical absorption and material sample.
Figure 2: Electrospray-ionization mass spectrum.
Figure 3: X-ray crystal structure obtained from a Na4Ag44(p-MBA)30 crystal.
Figure 4: Projected densities of states and orbital images.

Similar content being viewed by others

References

  1. Heiz, U. & Landman, U. (eds) Nanocatalysis (Springer, 2007)

  2. Anker, J. N. et al. Biosensing with plasmonic nanosensors. Nature Mater. 7, 442–453 (2008)

    Article  ADS  CAS  Google Scholar 

  3. Jin, R. et al. Controlling anisotropic nanoparticle growth through plasmon excitation. Nature 425, 487–490 (2003)

    Article  ADS  CAS  Google Scholar 

  4. Maier, S. A. et al. Plasmonics — a route to nanoscale optical devices. Adv. Mater. 13, 1501–1505 (2001)

    Article  CAS  Google Scholar 

  5. Noginov, M. A. et al. Demonstration of a spaser-based nanolaser. Nature 460, 1110–1112 (2009)

    Article  ADS  CAS  Google Scholar 

  6. Atwater, H. A. & Polman, A. Plasmonics for improved photovoltaic devices. Nature Mater. 9, 205–213 (2010)

    Article  ADS  CAS  Google Scholar 

  7. Arvizo, R. R. et al. Intrinsic therapeutic applications of noble metal nanoparticles: past, present and future. Chem. Soc. Rev. 41, 2943–2970 (2012)

    Article  CAS  Google Scholar 

  8. Jadzinsky, P. D., Calero, G., Ackerson, C. J., Bushnell, D. A. & Kornberg, R. D. Structure of a thiol monolayer-protected gold nanoparticle at 1.1 Å resolution. Science 318, 430–433 (2007)

    Article  ADS  CAS  Google Scholar 

  9. Heaven, M. W., Dass, A., White, P. S., Holt, K. M. & Murray, R. W. Crystal structure of the gold nanoparticle [N(C8H17)4][Au25(SCH2CH2Ph)18]. J. Am. Chem. Soc. 130, 3754–3755 (2008)

    Article  CAS  Google Scholar 

  10. Zhu, M., Aikens, C. M., Hollander, F. J., Schatz, G. C. & Jin, R. Correlating the crystal structure of a thiol-protected Au25 cluster and optical properties. J. Am. Chem. Soc. 130, 5883–5885 (2008)

    Article  CAS  Google Scholar 

  11. Qian, H., Eckenhoff, W. T., Zhu, Y., Pintauer, T. & Jin, R. Total structure determination of thiolate-protected Au38 nanoparticles. J. Am. Chem. Soc. 132, 8280–8281 (2010)

    Article  CAS  Google Scholar 

  12. Zeng, C. et al. Total structure of the golden nanocrystal Au36(SR)24 . Angew. Chem. Int. Edn 51, 13114–13118 (2012)

    Article  CAS  Google Scholar 

  13. Williams, R. The Geometrical Foundation of Natural Structure (Dover, New York, 1979)

    Google Scholar 

  14. Krätschmer, W., Lamb, L. D., Fostiropoulos, K. & Huffman, D. R. Solid C60: a new form of carbon. Nature 347, 354–358 (1990)

    Article  ADS  Google Scholar 

  15. Ebbesen, T. W. & Ajayan, P. M. Large-scale synthesis of carbon nanotubes. Nature 358, 220–222 (1992)

    Article  ADS  CAS  Google Scholar 

  16. Bethune, D. S. et al. Cobalt-catalysed growth of carbon nano-tubes with single-atomic-layer walls. Nature 363, 605–607 (1993)

    Article  ADS  CAS  Google Scholar 

  17. Murray, C. B., Norris, D. J. & Bawendi, M. G. Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites. J. Am. Chem. Soc. 115, 8706–8715 (1993)

    Article  CAS  Google Scholar 

  18. Brust, M., Walker, M., Bethell, D., Schiffrin, D. J. & Whyman, R. Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system. J. Chem. Soc. Chem. Commun. 1994, 801–802 (1994)

    Article  Google Scholar 

  19. Bakr, O. M. et al. Silver nanoparticles with broad multiband linear optical absorption. Angew. Chem. Int. Edn 48, 5921–5926 (2009)

    Article  CAS  Google Scholar 

  20. Harkness, K. M. et al. Ag44(SR)304−: a silver–thiolate superatom complex. Nanoscale 4, 4269–4274 (2012)

    Article  ADS  CAS  Google Scholar 

  21. Shichibu, Y. et al. Extremely high stability of glutathione-protected Au25 clusters against core etching. Small 3, 835–839 (2007)

    Article  CAS  Google Scholar 

  22. Cathcart, N. & Kitaev, V. Silver nanoclusters: single-stage scalable synthesis of mono-disperse species and their chiro-optical properties. J. Phys. Chem. C 114, 16010–16017 (2010)

    Article  CAS  Google Scholar 

  23. Dharmaratne, A. C., Krick, T. & Dass, A. Nanocluster size evolution studied by mass spectrometry in room temperature Au25(SR)18 synthesis. J. Am. Chem. Soc. 131, 13604–13605 (2009)

    Article  CAS  Google Scholar 

  24. Jana, N. R., Gearheart, L. & Murphy, C. J. Seeding growth for size control of 5−40 nm diameter gold nanoparticles. Langmuir 17, 6782–6786 (2001)

    Article  CAS  Google Scholar 

  25. Chakraborty, I. et al. The superstable 25-kDa monolayer protected silver nanoparticle: measurements and interpretation as an icosahedral Ag152(SCH2CH2Ph)60 cluster. Nano Lett. 12, 5861–5866 (2012)

    Article  ADS  CAS  Google Scholar 

  26. Dance, I. G. The structural chemistry of metal thiolate complexes. Polyhedron 5, 1037–1104 (1986)

    Article  CAS  Google Scholar 

  27. Herron, N., Calabrese, J. C., Farneth, W. E. & Wang, Y. Crystal structure and optical properties of Cd32S14(SC6H5)36•DMF4, a cluster with a 15 Å CdS core. Science 259, 1426–1428 (1993)

    Article  ADS  CAS  Google Scholar 

  28. Yoon, B. et al. Size-dependent structural evolution and chemical reactivity of gold clusters. ChemPhysChem 8, 157–161 (2007)

    Article  CAS  Google Scholar 

  29. Knight, W. D. et al. Electronic shell structure and abundances of sodium clusters. Phys. Rev. Lett. 52, 2141–2143 (1984)

    Article  ADS  CAS  Google Scholar 

  30. Yannouleas, C. & Landman, U. in Recent Progress in Orbital-Free Density Functional Theory (eds Wesolowski, T. A. & Wang, Y. A. ) 203–250 (World Scientific, 2013)

    Book  Google Scholar 

  31. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999)

    Article  ADS  CAS  Google Scholar 

  32. Perdew, J. P. in Electronic Structure of Solids '91 (eds Ziesche, P. & Eschrig, H. ) 11–20 (Akademie, 1991)

    Google Scholar 

  33. Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46, 6671–6687 (1992); Erratum. Phys. Rev. B 48, 4978–4978 (1993)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

The work at the University of Toledo was supported by NSF grants CBET-0955148 and CRIF-0840474 as well as by the Wright Center for Photovoltaics Innovation and Commercialization and the School of Solar and Advanced Renewable Energy. The work of B.Y. and U.L. was supported by the Office of Basic Energy Sciences of the US Department of Energy under contract no. FG05-86ER45234 and in part by a grant from the Air Force Office of Scientific Research. Computations were made at the GATECH Center for Computational Materials Science. We acknowledge F. Stellacci for discussions and the College of Natural Sciences and Mathematics Instrumentation Center at the University of Toledo for the use of X-ray diffraction instrumentation.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Toledo, Toledo, 43606, Ohio, USA

    Anil Desireddy, Brian E. Conn, Jingshu Guo, Bradley M. Monahan, Kristin Kirschbaum, Wendell P. Griffith & Terry P. Bigioni

  2. School of Physics, Georgia Institute of Technology, Atlanta, 30332-0430, Georgia, USA

    Bokwon Yoon, Robert N. Barnett & Uzi Landman

  3. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, 30332-0400, Georgia, USA

    Robert L. Whetten

  4. Department of Physics and Astronomy, University of Texas at San Antonio, San Antonio, 78249, Texas, USA

    Robert L. Whetten

  5. School of Solar and Advanced Renewable Energy, University of Toledo, Toledo, 43606, Ohio, USA

    Terry P. Bigioni

Authors
  1. Anil Desireddy
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Brian E. Conn
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jingshu Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bokwon Yoon
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Robert N. Barnett
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bradley M. Monahan
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Kristin Kirschbaum
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Wendell P. Griffith
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Robert L. Whetten
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Uzi Landman
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Terry P. Bigioni
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

T.P.B. conceived, directed and analysed all experimental research except for mass spectrometry, which W.P.G. directed and analysed, and X-ray diffraction, which K.K. directed and analysed. A.D., B.E.C. and B.M.M. performed all experimental work except for mass spectrometry, which J.G. performed. All computations and theoretical analyses were done by B.Y., R.N.B. and U.L. All authors contributed to the preparation of the manuscript.

Corresponding author

Correspondence to Terry P. Bigioni.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

The X-ray crystallographic coordinates have been deposited in the Cambridge Crystallographic Data Centre with CCDC number 949240.

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Figures 1-6, Supplementary Tables 1-8 and Supplementary References. (PDF 2554 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Desireddy, A., Conn, B., Guo, J. et al. Ultrastable silver nanoparticles. Nature 501, 399–402 (2013). https://doi.org/10.1038/nature12523

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature12523

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