Letter | Published:

High-spatial-resolution mapping of catalytic reactions on single particles

Nature volume 541, pages 511515 (26 January 2017) | Download Citation

Abstract

The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established1,2. But despite the growing availability of tools that enable detailed in situ characterization3, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces4,5, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy6,7 with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles—which contain metal atoms with low coordination numbers—are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.

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References

  1. 1.

    & Introduction to Surface Chemistry and Catalysis 2nd edn (Wiley, 2010)

  2. 2.

    , , & Identification of the “active sites” of a surface-catalyzed reaction. Science 273, 1688–1690 (1996)

  3. 3.

    & Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy. Nat. Chem. 4, 873–886 (2012)

  4. 4.

    et al. Quantitative 3D fluorescence imaging of single catalytic turnovers reveals spatiotemporal gradients in reactivity of zeolite H-ZSM-5 crystals upon steaming. J. Am. Chem. Soc. 137, 6559–6568 (2015)

  5. 5.

    et al. Single-molecule catalysis mapping quantifies site-specific activity and uncovers radial activity gradient on single 2D nanocrystals. J. Am. Chem. Soc. 135, 1845–1852 (2013)

  6. 6.

    , , , & Ultrabroadband infrared nanospectroscopic imaging. Proc. Natl Acad. Sci. USA 111, 7191–7196 (2014)

  7. 7.

    et al. Characterization of semiconductor materials using synchrotron radiation-based near-field infrared microscopy and nano-FTIR spectroscopy. Opt. Express 22, 17948–17958 (2014)

  8. 8.

    & Infrared and Raman imaging of heterogeneous catalysts. Chem. Soc. Rev. 39, 4615–4625 (2010)

  9. 9.

    et al. In Situ IR and X-ray high spatial-resolution microspectroscopy measurements of multistep organic transformation in flow microreactor catalyzed by Au nanoclusters. J. Am. Chem. Soc . 136, 3624–3629 (2014)

  10. 10.

    , & Infrared chemical nano-imaging: accessing structure, coupling, and dynamics on molecular length scales. J. Phys. Chem. Lett. 6, 1275–1284 (2015)

  11. 11.

    Infrared imaging and spectroscopy beyond the diffraction limit. Annu. Rev. Anal. Chem. (Palo Alto, Calif.) 8, 101–126 (2015)

  12. 12.

    , , , & Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nat. Nanotechnol. 7, 583–586 (2012)

  13. 13.

    et al. Nano-FTIR absorption spectroscopy of molecular fingerprints at 20 nm spatial resolution. Nano Lett. 12, 3973–3978 (2012)

  14. 14.

    , , & Separation of time-resolved phenomena in surface-enhanced Raman scattering of the photocatalytic reduction of p-nitrothiophenol. ChemPhysChem 16, 547–554 (2015)

  15. 15.

    et al. Tip-enhanced Raman spectroscopy – an interlaboratory reproducibility and comparison study. J. Raman Spectrosc. 45, 22–31 (2014)

  16. 16.

    , & Near-field study of the solid electrolyte interphase on a tin electrode. J. Phys. Chem. Lett. 6, 1126–1129 (2015)

  17. 17.

    , , , & Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references. Appl. Phys. Lett. 106, 023113 (2015)

  18. 18.

    , , & Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics. Nat. Commun. 5, 3587 (2014)

  19. 19.

    et al. Nano-chemical infrared imaging of membrane proteins in lipid bilayers. J. Am. Chem. Soc. 135, 18292–18295 (2013)

  20. 20.

    & High spatial resolution mapping of chemically-active self-assembled N-heterocyclic carbenes on Pt nanoparticles. Faraday Discuss. 188, 345–353 (2016)

  21. 21.

    et al. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold. Nat. Chem. 6, 409–414 (2014)

  22. 22.

    , , & Addressable carbene anchors for gold surfaces. J. Am. Chem. Soc. 135, 7418–7421 (2013)

  23. 23.

    et al. Modular bidentate hybrid NHC-thioether ligands for the stabilization of palladium nanoparticles in various solvents. Angew. Chem. Int. Ed. 55, 5856–5860 (2016)

  24. 24.

    , , & Preparation, modification, and crystallinity of aliphatic and aromatic carboxylic acid terminated self-assembled monolayers. Langmuir 18, 3980–3992 (2002)

  25. 25.

    , , , & 2/D2 isotopic exchange: a tool to characterize complex hydrogen interaction with carbon-supported ruthenium catalysts. Catal. Today 259, 9–18 (2016)

  26. 26.

    et al. Insights into the reactivity of supported Au nanoparticles: combining theory and experiments. Top. Catal. 44, 15–26 (2007)

  27. 27.

    & Mechanism of catalysis of hydrocarbon reactions by platinum surfaces. Nature 258, 580–583 (1975)

  28. 28.

    et al. Controlling the catalytic bond-breaking selectivity of Ni surfaces by step blocking. Nat. Mater. 4, 160–162 (2005)

  29. 29.

    et al. On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation. J. Catal. 223, 232–235 (2004)

  30. 30.

    et al. In situ surface-enhanced Raman spectroscopy study of plasmon-driven catalytic reactions of 4-nitrothiophenol under a controlled atmosphere. ChemCatChem 7, 1004–1010 (2015)

  31. 31.

    et al. Encapsulation of Au nanoparticles on a silicon wafer during thermal oxidation. J. Phys. Chem. C 117, 21577–21582 (2013)

  32. 32.

    , & Easily accessible chiral imidazolinium salts bearing two hydroxy-containing substituents as shift reagents and carbene precursors. Eur. J. Org. Chem. 2006, 5103–5109 (2006)

  33. 33.

    , , & N-heterocyclic carbenes with a N-2,4-dinitrophenyl substituent: comparison with PPh3 and IPr. Organometallics 31, 6995–7003 (2012)

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Acknowledgements

F.D.T. thanks the Director, Office of Science, Office of Basic Energy Sciences and the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy at LBNL (DE-AC02-05CH11231) for partial support of this work. We thank the M. Raschke group at the University of Colorado for collaborating on the development of the SINS endstation. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract number DE-AC02-05CH11231. W.J.W. thanks the NSF for a predoctoral fellowship (DGE 1106400), and the Arnold Group (UCB) for use of their infrared spectrometer.

Author information

Affiliations

  1. Department of Chemistry, University of California, Berkeley, California 94720, USA

    • Chung-Yeh Wu
    • , William J. Wolf
    •  & F. Dean Toste
  2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA

    • Chung-Yeh Wu
    • , William J. Wolf
    •  & F. Dean Toste
  3. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

    • Yehonatan Levartovsky
    •  & Elad Gross
  4. The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

    • Yehonatan Levartovsky
    •  & Elad Gross
  5. Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA

    • Hans A. Bechtel
    •  & Michael C. Martin

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Contributions

E.G. and F.D.T. conceived the idea and co-wrote the paper. C.-Y.W. and W.J.W. prepared the carbene ligands and attached them to Pt and Au surfaces. Y.L. analysed the XPS measurements. H.A.B. and M.C.M. designed the SINS beamline and assisted in conducting the SINS measurements and analysing the data. E.G. performed the SINS experiments and analysed the data. All authors contributed to the overall scientific interpretation and edited the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to F. Dean Toste or Elad Gross.

Reviewer Information

Nature thanks C. Campbell, G. Rothenberg, F. Tao, B. Weckhuysen and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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DOI

https://doi.org/10.1038/nature20795

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