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:

Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution

Nature Nanotechnology volume 12, pages 132–136 (2017)Cite this article

Subjects

Abstract

An atomic- and molecular-level understanding of heterogeneous catalysis is required to characterize the nature of active sites and improve the rational design of catalysts1,2,3. Achieving this level of characterization requires techniques that can correlate catalytic performances to specific surface structures, so as to avoid averaging effects1. Tip-enhanced Raman spectroscopy4,5,6,7 combines scanning probe microscopy with plasmon-enhanced Raman scattering and provides simultaneous topographical and chemical information at the nano/atomic scale from ambient8,9,10 to ultrahigh-vacuum11,12 and electrochemical environments13,14. Therefore, it has been used to monitor catalytic reactions15,16,17,18 and is proposed to correlate the local structure and function of heterogeneous catalysts19. Bimetallic catalysts, such as Pd–Au, show superior performance in various catalytic reactions20,21, but it has remained challenging to correlate structure and reactivity because of their structural complexity. Here, we show that TERS can chemically and spatially probe the site-specific chemical (electronic and catalytic) and physical (plasmonic) properties of an atomically well-defined Pd(sub-monolayer)/Au(111) bimetallic model catalyst at 3 nm resolution in real space using phenyl isocyanide as a probe molecule (Fig. 1a). We observe a weakened N≡C bond and enhanced reactivity of phenyl isocyanide adsorbed at the Pd step edge compared with that at the Pd terrace. Density functional theory corroborates these observations by revealing a higher d-band electronic profile for the low-coordinated Pd step edge atoms. The 3 nm spatial resolution we demonstrate here is the result of an enhanced electric field and distinct electronic properties at the step edges.

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: TERS study of a Pd/Au(111) bimetallic model catalyst.
Figure 2: TERS spectra of PIC.
Figure 3: TERS images of a Pd/Au(111) bimetallic surface.
Figure 4: Electronic properties of Pd step edges.

Similar content being viewed by others

References

  1. Buurmans, I. L. C. & Weckhuysen, B. M. Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy. Nat. Chem. 4, 873–886 (2012).

    Article  CAS  Google Scholar 

  2. Ding, K. et al. Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts. Science 350, 189–192 (2015).

    Article  CAS  Google Scholar 

  3. Chen, G. et al. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation. Science 344, 495–499 (2014).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  5. Anderson, M. S. Locally enhanced Raman spectroscopy with an atomic force microscope. Appl. Phys. Lett 76, 3130–3132 (2000).

    Article  CAS  Google Scholar 

  6. Hayazawa, N., Inouye, Y., Sekkat, Z. & Kawata, S. Metallized tip amplification of near-field Raman scattering. Opt. Commun. 183, 333–336 (2000).

    Article  CAS  Google Scholar 

  7. Pettinger, B., Schambach, P., Villagómez, C. J. & Scott, N. Tip-enhanced Raman spectroscopy: near-fields acting on a few molecules. Annu. Rev. Phys. Chem. 63, 379–399 (2012).

    Article  CAS  Google Scholar 

  8. Berweger, S. et al. Optical nanocrystallography with tip-enhanced phonon Raman spectroscopy. Nat. Nanotech. 4, 496–499 (2009).

    Article  CAS  Google Scholar 

  9. Liu, Z. et al. Revealing the molecular structure of single-molecule junctions in different conductance states by fishing-mode tip-enhanced Raman spectroscopy. Nat. Commun. 2, 305 (2011).

    Article  Google Scholar 

  10. Yano, T. A. et al. Tip-enhanced nano-Raman analytical imaging of locally induced strain distribution in carbon nanotubes. Nat. Commun. 4, 2592 (2013).

    Article  Google Scholar 

  11. Zhang, R. et al. Chemical mapping of a single molecule by plasmon-enhanced Raman scattering. Nature 498, 82–86 (2013).

    Article  CAS  Google Scholar 

  12. Jiang, S. et al. Distinguishing adjacent molecules on a surface using plasmon-enhanced Raman scattering. Nat. Nanotech. 10, 865–869 (2015).

    Article  CAS  Google Scholar 

  13. Zeng, Z.-C. et al. Electrochemical tip-enhanced Raman spectroscopy. J. Am. Chem. Soc. 137, 11928–11931 (2015).

    Article  CAS  Google Scholar 

  14. Kurouski, D., Mattei, M. & Van Duyne, R. P. Probing redox reactions at the nanoscale with electrochemical tip-enhanced Raman spectroscopy. Nano Lett. 15, 7956–7962 (2015).

    Article  CAS  Google Scholar 

  15. van Schrojenstein Lantman, E. M., Deckert-Gaudig, T., Mank, A. J. G., Deckert, V. & Weckhuysen, B. M. Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nat. Nanotech. 7, 583–586 (2012).

    Article  CAS  Google Scholar 

  16. Sun, M., Zhang, Z., Zheng, H. & Xu, H. In-situ plasmon-driven chemical reactions revealed by high vacuum tip-enhanced Raman spectroscopy. Sci. Rep. 2, 647 (2012).

    Article  Google Scholar 

  17. Kumar, N., Stephanidis, B., Zenobi, R., Wain, A. J. & Roy, D. Nanoscale mapping of catalytic activity using tip-enhanced Raman spectroscopy. Nanoscale 7, 7133–7137 (2015).

    Article  CAS  Google Scholar 

  18. 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 

  19. Hartman, T., Wondergem, C. S., Kumar, N., van den Berg, A. & Weckhuysen, B. M. Surface- and tip-enhanced Raman spectroscopy in catalysis. J. Phys. Chem. Lett. 7, 1570–1584 (2016).

    Article  CAS  Google Scholar 

  20. Chen, M., Kumar, D., Yi, C.-W. & Goodman, D. W. The promotional effect of gold in catalysis by palladium-gold. Science 310, 291–293 (2005).

    Article  CAS  Google Scholar 

  21. Zhang, H., Watanabe, T., Okumura, M., Haruta, M. & Toshima, N . Catalytically highly active top gold atom on palladium nanocluster. Nat. Mater. 11, 49–52 (2012).

    Article  Google Scholar 

  22. Nenajdenko, V. G . (ed.) Isocyanide Chemistry: Applications in Synthesis and Material Science (Wiley-VCH, 2012).

    Book  Google Scholar 

  23. Hu, J., Tanabe, M., Sato, J., Uosaki, K. & Ikeda, K. Effects of atomic geometry and electronic structure of platinum surfaces on molecular adsorbates studied by gap-mode SERS. J. Am. Chem. Soc. 136, 10299–10307 (2014).

    Article  CAS  Google Scholar 

  24. Hu, J., Hoshi, N., Uosaki, K. & Ikeda, K. Vibrational spectroscopic observation of atomic-scale local surface sites using site-selective signal enhancement. Nano Lett. 15, 7982–7986 (2015).

    Article  CAS  Google Scholar 

  25. Lazar, M. & Angelici, R. J. Gold metal-catalyzed reactions of isocyanides with primary amines and oxygen: analogies with reactions of isocyanides in transition metal complexes. J. Am. Chem. Soc. 128, 10613–10620 (2006).

    Article  CAS  Google Scholar 

  26. Stapleton, J. J. et al. Self-assembly, characterization, and chemical stability of isocyanide-bound molecular wire monolayers on gold and palladium surfaces. Langmuir 21, 11061–11070 (2005).

    Article  CAS  Google Scholar 

  27. Zhang, W. H. et al. Nanoscale roughness on metal surfaces can increase tip-enhanced Raman scattering by an order of magnitude. Nano Lett. 7, 1401–1405 (2007).

    Article  CAS  Google Scholar 

  28. Barbry, M. et al. Atomistic near-field nanoplasmonics: reaching atomic-scale resolution in nanooptics. Nano Lett. 15, 3410–3419 (2015).

    Article  CAS  Google Scholar 

  29. Hammer, B. & Nørskov, J. K. Theoretical surface science and catalysis—calculations and concepts. Adv. Catal. 45, 71–129 (2000).

    CAS  Google Scholar 

  30. Kresse, G., Gil, A. & Sautet, P. Significance of single-electron energies for the description of CO on Pt(111). Phys. Rev. B 68, 073401 (2003).

    Article  Google Scholar 

  31. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

    Article  Google Scholar 

Download references

Acknowledgements

The authors acknowledge support from MOST (2016YFA0200601, 2013CB933703 and 2011YQ03012400), NSFC (21633005, 21227004, 21321062 and J1310024) and MOE (IRT13036). The authors thank J.M. Feliu, N. Zheng, D.-Y. Wu, M. Zhang, X.-G. Zhang and A. Terfort for discussions, S. Mo for assistance with ICP-MS measurements and Y. Zheng for help with XPS measurements. The authors acknowledge the National Supercomputer Center in Guangzhou for Tianhe-2 CPU time and assistance. C.T.W. acknowledges support from the PCOSS fellowship programme.

Author information

Author notes

  1. Jin-Hui Zhong and Xi Jin: These authors contributed equally to this work

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), MOE Key Laboratory of Spectrochemical Analysis & Instrumentation, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Jin-Hui Zhong, Xi Jin, Xiang Wang, Hai-Sheng Su & Bin Ren

  2. Department of Physics, Xiamen University, Xiamen, 361005, China

    Lingyan Meng & Zhi-Lin Yang

  3. Department of Chemical Engineering, University of South Carolina, Columbia, 29208, South Carolina, USA

    Christopher T. Williams

Authors
  1. Jin-Hui Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xi Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lingyan Meng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hai-Sheng Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zhi-Lin Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Christopher T. Williams
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Bin Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

B.R. supervised the project. J.-H.Z. and B.R. conceived the ideas. J.-H.Z., X.W. and H.-S.S performed the experiments. X.J. performed electronic structure and vibrational frequency calculations. L.M. and Z.-L.Y. performed electromagnetic field simulations. C.T.W. helped with experiments and analysis. All authors contributed to data interpretation and writing of the manuscript.

Corresponding author

Correspondence to Bin Ren.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2613 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhong, JH., Jin, X., Meng, L. et al. Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution. Nature Nanotech 12, 132–136 (2017). https://doi.org/10.1038/nnano.2016.241

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2016.241

This article is cited by

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