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.

Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy

Nature Nanotechnology volume 7, pages 583–586 (2012)Cite this article

Subjects

Abstract

Heterogeneous catalysts play a pivotal role in the chemical industry, but acquiring molecular insights into functioning catalysts remains a significant challenge1,2,3,4. Recent advances in micro-spectroscopic approaches have allowed spatiotemporal information to be obtained on the dynamics of single active sites and the diffusion of single molecules5,6. However, these methods lack nanometre-scale spatial resolution and/or require the use of fluorescent labels. Here, we show that time-resolved tip-enhanced Raman spectroscopy can monitor photocatalytic reactions at the nanoscale. We use a silver-coated atomic force microscope tip to both enhance the Raman signal and to act as the catalyst. The tip is placed in contact with a self-assembled monolayer of p-nitrothiophenol molecules adsorbed on gold nanoplates. A photocatalytic reduction process is induced at the apex of the tip with green laser light, while red laser light is used to monitor the transformation process during the reaction. This dual-wavelength approach can also be used to observe other molecular effects such as monolayer diffusion.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

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

Figure 1: Schematic overview of the experimental set-up.
Figure 2: Monitoring the photocatalytic reaction with SERS.
Figure 3: Time-dependent TERS measurements on a gold nanoplate substrate.
Figure 4: Time-dependent TERS measurement before and after reaction.

References

  1. Roeffaers, M. B. J. et al. Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting. Nature 439, 572–575 (2006).

    Article  CAS  Google Scholar 

  2. Xu, W., Kong, J. S., Yeh, Y-T. E. & Chen, P. Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics. Nature Mater. 7, 992–996 (2008).

    Article  CAS  Google Scholar 

  3. Weckhuysen, B. M. Chemical imaging of spatial heterogeneities in catalytic solids at different length and time scales. Angew. Chem. Int. Ed. 48, 4910–4943 (2009).

    Article  CAS  Google Scholar 

  4. Lamberti, C., Zecchina, A., Groppo, E. & Bordiga, S. Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy. Chem. Soc. Rev. 39, 4951–5001 (2010).

    Article  CAS  Google Scholar 

  5. De Cremer, G., Sels, B. F., De Vos, D. E., Hofkens, J. & Roeffaers, M. B. J. Fluorescence micro(spectro)scopy as a tool to study catalytic materials in action. Chem. Soc. Rev. 39, 4703–4717 (2010).

    Article  CAS  Google Scholar 

  6. Kim, H., Kosuda, K. M., Van Duyne, R. P. & Stair, P. C. Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions. Chem. Soc. Rev. 39, 4820–4844 (2010).

    Article  CAS  Google Scholar 

  7. Singh, J., Lamberti, C. & van Bokhoven, J. A. Advanced X-ray absorption and emission spectroscopy: in situ catalytic studies. Chem. Soc. Rev. 39, 4754–4766 (2010).

    Article  CAS  Google Scholar 

  8. Kawata, S., Inouye, Y. & Verma, P. Plasmonics for near-field nano-imaging and superlensing. Nature Photon. 3, 388–394 (2009).

    Article  CAS  Google Scholar 

  9. Stöckle, R. M., Doug Suh, Y., Deckert, V. & Zenobi, R. Nanoscale chemical analysis by tip-enhanced Raman spectroscopy. Chem. Phys. Lett. 318, 131–136 (2000).

    Article  Google Scholar 

  10. Pettinger, B., Ren, B., Picardi, G., Schuster, R. & Ertl, G. Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy. Phys. Rev. Lett. 92, 096101 (2004).

    Article  Google Scholar 

  11. Bailo, E. & Deckert, V. Tip-enhanced Raman scattering. Chem. Soc. Rev. 37, 921–930 (2008).

    Article  CAS  Google Scholar 

  12. Yeo, B-S., Stadler, J., Schmid, T., Zenobi, R. & Zhang, W. Tip-enhanced Raman spectroscopy—its status, challenges and future directions. Chem. Phys. Lett. 472, 1–13 (2009).

    Article  CAS  Google Scholar 

  13. Domke, K. F. & Pettinger, B. Studying surface chemistry beyond the diffraction limit: 10 years of TERS. ChemPhysChem 11, 1365–1373 (2010).

    Article  CAS  Google Scholar 

  14. Yang, Z., Aizpurua, J. & Xu, H. Electromagnetic field enhancement in TERS configurations. J. Raman Spectrosc. 40, 1343–1348 (2009).

    Article  CAS  Google Scholar 

  15. Fokas, C. & Deckert, V. Towards in situ Raman microscopy of single catalytic sites. Appl. Spectrosc. 56, 192–199 (2002).

    Article  CAS  Google Scholar 

  16. Domke, K. F. & Pettinger, B. In situ discrimination between axially complexed and ligand-free Co porphyrin on Au(111) with tip-enhanced Raman spectroscopy. ChemPhysChem 10, 1794–1798 (2009).

    Article  CAS  Google Scholar 

  17. Kim, K., Lee, I. & Lee, S. J. Photolytic reduction of 4-nitrobenzenethiol on Au mediated via Ag nanoparticles. Chem. Phys. Lett. 377, 201–204 (2003).

    Article  CAS  Google Scholar 

  18. Kim, K. et al. Visible laser-induced photoreduction of silver 4-nitrobenzenethiolate revealed by Raman scattering spectroscopy. J. Raman Spectrosc. 41, 187–192 (2010).

    Article  CAS  Google Scholar 

  19. Sun, S., Birke, R. L., Lombardi, J. R., Leung, K. P. & Genack, A. Z. Photolysis of p-nitrobenzoic acid on roughened silver surfaces. J. Phys. Chem. 92, 5965–5972 (1988).

    Article  CAS  Google Scholar 

  20. Osawa, M., Matsuda, N., Yoshii, K. & Uchida, I. Charge transfer resonance Raman process in surface-enhanced Raman scattering from p-aminothiophenol adsorbed on silver: Herzberg–Teller contribution. J. Phys. Chem. 98, 12702–12707 (1994).

    Article  CAS  Google Scholar 

  21. Huang, Y-F. et al. When the signal is not from the original molecule to be detected: chemical transformation of para-aminothiophenol on Ag during the SERS measurement. J. Am. Chem. Soc. 132, 9244–9246 (2010).

    Article  CAS  Google Scholar 

  22. Kim, K., Kim, L. K., Lee, H. B. & Shin, K. S. Similarity and dissimilarity in surface-enhanced Raman scattering of 4-aminobenzenethiol, 4,4′-dimercaptoazobenzene, and 4,4′-dimercaptohydrazobenzene on Ag. J. Phys. Chem. C 116, 11635–11642 (2012).

    Article  CAS  Google Scholar 

  23. Huang, Y-F. et al. Surface-enhanced Raman spectroscopic study of p-aminothiophenol. Phys. Chem. Chem. Phys. 14, 8485–8497 (2012).

    Article  CAS  Google Scholar 

  24. Skadtchenko, B. O. & Aroca, R. Surface-enhanced Raman scattering of p-nitrothiophenol molecular vibrations of its silver salt and the surface complex formed on silver islands and colloids. Spectrochim. Acta A 57, 1009–1016 (2001).

    Article  Google Scholar 

  25. Deckert-Gaudig, T. & Deckert, V. Ultraflat transparent gold nanoplates—ideal substrates for tip-enhanced Raman scattering experiments. Small 5, 432–436 (2009).

    Article  CAS  Google Scholar 

  26. Vericat, C., Vela, M. E., Benitez, G., Carro, P. & Salvarezza, R. C. Self-assembled monolayers of thiols and dithiols on gold: new challenges for a well-known system. Chem. Soc. Rev. 39, 1805–1834 (2010).

    Article  CAS  Google Scholar 

  27. Rasmussen, A. & Deckert, V. Surface- and tip-enhanced Raman scattering of DNA components. J. Raman Spectrosc. 37, 311–317 (2006).

    Article  CAS  Google Scholar 

  28. Kudelski, A. & Pettinger, B. Fluctuations of surface-enhanced Raman spectra of CO adsorbed on gold substrates. Chem. Phys. Lett. 383, 76–79 (2004).

    Article  CAS  Google Scholar 

  29. Neascu, C. C., Dreyer, J., Behr, N. & Raschke, M. B. Scanning-probe Raman spectroscopy with single-molecule sensitivity. Phys. Rev. B 73, 193406 (2006).

    Article  Google Scholar 

  30. Agapov, R. L., Malkovskiy, A. V., Sokolov, A. P. & Foster, M. D. Prolonged blinking with TERS probes. J. Phys. Chem. C 115, 8900–8905 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by NanoNextNL of the Dutch ministry EL&I and 130 partners. The authors also thank the Netherlands Research School Combination–Catalysis (NRSC-C) and Dutch National Science Foundation (NWO-CW Top research grant) for financial support.

Author information

Authors and Affiliations

  1. Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterial Science, Utrecht University, Universiteitsweg 99, Utrecht, 3584 CG, The Netherlands

    Evelien M. van Schrojenstein Lantman, Arjan J. G. Mank & Bert M. Weckhuysen

  2. Institute of Photonic Technology, Albert-Einstein-Strasse 9, Jena, D-07745, Germany

    Tanja Deckert-Gaudig & Volker Deckert

  3. Molecular and Surface Analysis, Philips Innovation Services, High Tech Campus 11, Eindhoven, 5656 AE, The Netherlands

    Arjan J. G. Mank

  4. Physical Chemistry, Friedrich-Schiller University Jena, Helmholtzweg, 07743, Jena, Germany

    Volker Deckert

Authors
  1. Evelien M. van Schrojenstein Lantman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tanja Deckert-Gaudig
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Arjan J. G. Mank
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Volker Deckert
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bert M. Weckhuysen
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

E.M.v.S.L., T.D.-G. and A.J.G.M. carried out the experiments and E.M.v.S.L. performed data processing. V.D. and T.D.-G. developed the experimental set-up. E.M.v.S.L., A.J.G.M. and B.M.W. designed the experiments. All authors contributed to the discussion of the results as well as to the preparation and writing of the manuscript. The research was directed by B.M.W.

Corresponding authors

Correspondence to Volker Deckert or Bert M. Weckhuysen.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 822 kb)

Supplementary Movie S1

Supplementary Movie S1 (MOV 4136 kb)

Supplementary Movie S2

Supplementary Movie S2 (MOV 1496 kb)

Supplementary Movie S3

Supplementary Movie S3 (MOV 1629 kb)

Supplementary Movie S4

Supplementary Movie S4 (MOV 1853 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

van Schrojenstein Lantman, E., Deckert-Gaudig, T., Mank, A. et al. Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nature Nanotech 7, 583–586 (2012). https://doi.org/10.1038/nnano.2012.131

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2012.131

This article is cited by

Search

Advanced search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research