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:

Imaging the electrocatalytic activity of single nanoparticles

Abstract

The electrocatalytic properties of nanoparticles depend on their size, shape and composition1,2. These properties are typically probed by measuring the total electrocatalytic reaction current of a large number of nanoparticles, but this approach is time-consuming and can only measure the average catalytic activity of the nanoparticles under study. However, the identification of new catalysts requires the ability to rapidly measure the properties of nanoparticles synthesized under various conditions and, ideally, to measure the electrocatalytic activity of individual nanoparticles. Here, we show that a plasmonic-based electrochemical current-imaging technique3 can simultaneously image and quantify the electrocatalytic reactions of an array of 1.6 × 105 platinum nanoparticles printed on an electrode surface, which could facilitate high-throughput screening of the catalytic activities of nanoparticles. We also show that the approach can be used to image the electrocatalytic reaction current and measure the cyclic voltammograms of single nanoparticles.

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

Access options

Buy this article

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

Figure 1: P-ECi current image of a platinum nanoparticle microarray.
Figure 2: Platinum nanoparticle microarray with different surface densities.
Figure 3: Experimental and simulated SPR images of platinum nanoparticles.
Figure 4: Electrocatalytic reaction of a single platinum nanoparticle.
Figure 5: Statistical analysis of single platinum nanoparticle electrocatalysis.

Similar content being viewed by others

References

  1. Zhou, Z. Y., Tian, N., Li, J. T., Broadwell, I. & Sun, S. G. Nanomaterials of high surface energy with exceptional properties in catalysis and energy storage. Chem. Soc. Rev. 40, 4167–4185 (2011).

    Article  CAS  Google Scholar 

  2. Shan, X. N. et al. Measuring surface charge density and particle height using surface plasmon resonance technique. Anal. Chem. 82, 234–240 (2010).

    Article  CAS  Google Scholar 

  3. Shan, X. N., Patel, U., Wang, S. P., Iglesias, R. & Tao, N. J. Imaging local electrochemical current via surface plasmon resonance. Science 327, 1363–1366 (2010).

    Article  CAS  Google Scholar 

  4. Bard, A. J. et al. Chemical imaging of surfaces with the scanning electrochemical microscope. Science 254, 68–74 (1991).

    Article  CAS  Google Scholar 

  5. Lu, X., Wang, Q. & Liu, X. Review: recent applications of scanning electrochemical microscopy to the study of charge transfer kinetics. Anal. Chim. Acta 601, 10–25 (2007).

    Article  CAS  Google Scholar 

  6. Xiao, X. Y. & Bard, A. J. Observing single nanoparticle collisions at an ultramicroelectrode by electrocatalytic amplification. J. Am. Chem. Soc. 129, 9610–9612 (2007).

    Article  CAS  Google Scholar 

  7. Xiao, X. Y., Fan, F. R. F., Zhou, J. P. & Bard, A. J. Current transients in single nanoparticle collision events. J. Am. Chem. Soc. 130, 16669–16677 (2008).

    Article  CAS  Google Scholar 

  8. Li, Y. X., Cox, J. T. & Zhang, B. Electrochemical responses and electrocatalysis at single Au nanoparticles. J. Am. Chem. Soc. 132, 3047–3054 (2010).

    Article  CAS  Google Scholar 

  9. Zhou, X. et al. Quantitative super-resolution imaging uncovers reactivity patterns on single nanocatalysts. Nature Nanotech. 7, 237–241 (2012).

    Article  CAS  Google Scholar 

  10. Foley, K. J., Shan, X. & Tao, N. J. Surface impedance imaging technique. Anal. Chem. 80, 5146–5151 (2008).

    Article  CAS  Google Scholar 

  11. Shan, X. N., Wang, S. P., Wang, W. & Tao, N. J. Plasmonic-based imaging of local square wave voltammetry. Anal. Chem. 83, 7394–7399 (2011).

    Article  CAS  Google Scholar 

  12. Wang, S. P., Huang, X. P., Shan, X. N., Foley, K. J. & Tao, N. J. Electrochemical surface plasmon resonance: basic formalism and experimental validation. Anal. Chem. 82, 935–941 (2010).

    Article  CAS  Google Scholar 

  13. Boyer, D., Tamarat, P., Maali, A., Lounis, B. & Orrit, M. Photothermal imaging of nanometer-sized metal particles among scatterers. Science 297, 1160–1163 (2002).

    Article  CAS  Google Scholar 

  14. Gaiduk, A., Yorulmaz, M., Ruijgrok, P. V. & Orrit, M. Room-temperature detection of a single molecule's absorption by photothermal contrast. Science 330, 353–356 (2010).

    Article  CAS  Google Scholar 

  15. Huang, M. H. et al. Alternate assemblies of platinum nanoparticles and metalloporphyrins as tunable electrocatalysts for dioxygen reduction. Langmuir 21, 323–329 (2005).

    Article  CAS  Google Scholar 

  16. Rothenhausler, B. & Knoll, W. Surface-plasmon microscopy. Nature 332, 615–617 (1988).

    Article  Google Scholar 

  17. Huang, B., Yu, F. & Zare, R. N. Surface plasmon resonance imaging using a high numerical aperture microscope objective. Anal. Chem. 79, 2979–2983 (2007).

    Article  CAS  Google Scholar 

  18. Wang, S. et al. Label-free imaging, detection, and mass measurement of single viruses by surface plasmon resonance. Proc. Natl Acad. Sci. USA 107, 16028–16032 (2010).

    Article  CAS  Google Scholar 

  19. Wang, L., Gu, Y., Hu, X. & Gong, Q. Long-range surface plasmon polariton modes with a large field localized in a nanoscale gap. Appl. Phys. B 104, 919–924 (2011).

    Article  CAS  Google Scholar 

  20. Zayats, A. V., Smolyaninov, I. I. & Maradudin, A. A. Nano-optics of surface plasmon polaritons. Phys. Rep. Rev. Sec. Phys. Lett. 408, 131–314 (2005).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Science Foundation (CHE-1105588), the National Natural Science Foundation of China (no. 11121091), the National Basic Research Program of China (no. 2011CB935704) and the Natural Science Foundation of China (no. 20975060). I.D.P. thanks the Ramony Cajal program from the Spanish Government and EU International Reintegration Grant (FP7-PEOPLE-2010-RG-277182) for financial support. The authors thank Zhengtao Deng for his help to obtain TEM images of platinum nanoparticle.

Author information

Authors and Affiliations

Authors

Contributions

X.N.S. carried out the experiments and analysed the experimental data. I.D.P., P.V., L.Z., W.W., J.L. and J.H.L. helped with sample preparation. S.W. helped with instrumentation. L.J.W., Y.G. and Q.H.G. carried out theoretical simulations. N.J.T. conceived the project. X.N.S. and N.J.T. wrote the paper.

Corresponding authors

Correspondence to Ying Gu, Jinghong Li or Nongjian Tao.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 983 kb)

Supplementary Movie S1

Supplementary Movie S1 (AVI 15325 kb)

Supplementary Movie S2

Supplementary Movie S2 (AVI 3032 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shan, X., Díez-Pérez, I., Wang, L. et al. Imaging the electrocatalytic activity of single nanoparticles. Nature Nanotech 7, 668–672 (2012). https://doi.org/10.1038/nnano.2012.134

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2012.134

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