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

Abstract

We report 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 established. But despite the growing availability of tools that enable detailed in situ characterization, 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 surfaces, 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 nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, 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 carbenemore » molecules.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [1];  [2]
  1. Univ. of California, Berkeley, CA (United States). Department of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Hebrew Univ. of Jerusalem (Israel). Institute of Chemistry and The Center for Nanoscience and Nanotechnology
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1439214
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Volume: 541; Journal Issue: 7638; Related Information: © 2017 Macmillan Publishers Limited. All rights reserved.; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Chung-Yeh, Wolf, William J., Levartovsky, Yehonatan, Bechtel, Hans A., Martin, Michael C., Toste, F. Dean, and Gross, Elad. High-spatial-resolution mapping of catalytic reactions on single particles. United States: N. p., 2017. Web. doi:10.1038/nature20795.
Wu, Chung-Yeh, Wolf, William J., Levartovsky, Yehonatan, Bechtel, Hans A., Martin, Michael C., Toste, F. Dean, & Gross, Elad. High-spatial-resolution mapping of catalytic reactions on single particles. United States. doi:10.1038/nature20795.
Wu, Chung-Yeh, Wolf, William J., Levartovsky, Yehonatan, Bechtel, Hans A., Martin, Michael C., Toste, F. Dean, and Gross, Elad. Thu . "High-spatial-resolution mapping of catalytic reactions on single particles". United States. doi:10.1038/nature20795. https://www.osti.gov/servlets/purl/1439214.
@article{osti_1439214,
title = {High-spatial-resolution mapping of catalytic reactions on single particles},
author = {Wu, Chung-Yeh and Wolf, William J. and Levartovsky, Yehonatan and Bechtel, Hans A. and Martin, Michael C. and Toste, F. Dean and Gross, Elad},
abstractNote = {We report 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 established. But despite the growing availability of tools that enable detailed in situ characterization, 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 surfaces, 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 nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, 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.},
doi = {10.1038/nature20795},
journal = {Nature (London)},
issn = {0028-0836},
number = 7638,
volume = 541,
place = {United States},
year = {2017},
month = {1}
}

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Cited by: 43 works
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Works referenced in this record:

High spatial resolution mapping of chemically-active self-assembled N-heterocyclic carbenes on Pt nanoparticles
journal, January 2016


Controlling the catalytic bond-breaking selectivity of Ni surfaces by step blocking
journal, January 2005

  • Vang, Ronnie T.; Honkala, Karoliina; Dahl, Søren
  • Nature Materials, Vol. 4, Issue 2
  • DOI: 10.1038/nmat1311

Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references
journal, January 2015

  • Mastel, Stefan; Govyadinov, Alexander A.; de Oliveira, Thales V. A. G.
  • Applied Physics Letters, Vol. 106, Issue 2
  • DOI: 10.1063/1.4905507

IR Near-Field Study of the Solid Electrolyte Interphase on a Tin Electrode
journal, March 2015

  • Ayache, Maurice; Lux, Simon Franz; Kostecki, Robert
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00263

Mechanism of catalysis of hydrocarbon reactions by platinum surfaces
journal, December 1975

  • Somorjai, G. A.; Blakely, D. W.
  • Nature, Vol. 258, Issue 5536
  • DOI: 10.1038/258580a0

Tip-enhanced Raman spectroscopy - an interlaboratory reproducibility and comparison study: TERS interlaboratory comparison
journal, January 2014

  • Blum, Carolin; Opilik, Lothar; Atkin, Joanna M.
  • Journal of Raman Spectroscopy, Vol. 45, Issue 1
  • DOI: 10.1002/jrs.4423

Preparation, Modification, and Crystallinity of Aliphatic and Aromatic Carboxylic Acid Terminated Self-Assembled Monolayers
journal, May 2002

  • Arnold, Ralf; Azzam, Waleed; Terfort, Andreas
  • Langmuir, Vol. 18, Issue 10
  • DOI: 10.1021/la0117000

Encapsulation of Au Nanoparticles on a Silicon Wafer During Thermal Oxidation
journal, October 2013

  • Bowker, M.; Crouch, J. J.; Carley, A. F.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 41
  • DOI: 10.1021/jp4074043

Infrared Imaging and Spectroscopy Beyond the Diffraction Limit
journal, July 2015


Insights into the reactivity of supported Au nanoparticles: combining theory and experiments
journal, June 2007

  • Janssens, Ton V. W.; Clausen, Bjerne S.; Hvolbæk, Britt
  • Topics in Catalysis, Vol. 44, Issue 1-2
  • DOI: 10.1007/s11244-007-0335-3

Identification of the "Active Sites" of a Surface-Catalyzed Reaction
journal, September 1996


Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012

  • Buurmans, Inge L. C.; Weckhuysen, Bert M.
  • Nature Chemistry, Vol. 4, Issue 11
  • DOI: 10.1038/nchem.1478

Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics
journal, April 2014

  • Pollard, Benjamin; Muller, Eric A.; Hinrichs, Karsten
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4587

Infrared and Raman imaging of heterogeneous catalysts
journal, January 2010

  • Stavitski, Eli; Weckhuysen, Bert M.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00064g

Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold
journal, March 2014

  • Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.
  • Nature Chemistry, Vol. 6, Issue 5
  • DOI: 10.1038/nchem.1891

Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy
journal, August 2012

  • van Schrojenstein Lantman, Evelien M.; Deckert-Gaudig, Tanja; Mank, Arjan J. G.
  • Nature Nanotechnology, Vol. 7, Issue 9
  • DOI: 10.1038/nnano.2012.131

Addressable Carbene Anchors for Gold Surfaces
journal, May 2013

  • Zhukhovitskiy, Aleksandr V.; Mavros, Michael G.; Van Voorhis, Troy
  • Journal of the American Chemical Society, Vol. 135, Issue 20
  • DOI: 10.1021/ja401965d

H2/D2 isotopic exchange: A tool to characterize complex hydrogen interaction with carbon-supported ruthenium catalysts
journal, January 2016


Characterization of semiconductor materials using synchrotron radiation-based near-field infrared microscopy and nano-FTIR spectroscopy
journal, January 2014

  • Hermann, Peter; Hoehl, Arne; Ulrich, Georg
  • Optics Express, Vol. 22, Issue 15
  • DOI: 10.1364/OE.22.017948

Single-Molecule Catalysis Mapping Quantifies Site-Specific Activity and Uncovers Radial Activity Gradient on Single 2D Nanocrystals
journal, January 2013

  • Andoy, Nesha May; Zhou, Xiaochun; Choudhary, Eric
  • Journal of the American Chemical Society, Vol. 135, Issue 5
  • DOI: 10.1021/ja309948y

Nano-FTIR Absorption Spectroscopy of Molecular Fingerprints at 20 nm Spatial Resolution
journal, July 2012

  • Huth, Florian; Govyadinov, Alexander; Amarie, Sergiu
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301159v

Ultrabroadband infrared nanospectroscopic imaging
journal, May 2014

  • Bechtel, H. A.; Muller, E. A.; Olmon, R. L.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 20
  • DOI: 10.1073/pnas.1400502111

N-Heterocyclic Carbenes with a N -2,4-Dinitrophenyl Substituent: Comparison with PPh 3 and IPr
journal, September 2012

  • Sato, Tetsuo; Hirose, Yoichi; Yoshioka, Daisuke
  • Organometallics, Vol. 31, Issue 19
  • DOI: 10.1021/om300814f

In Situ IR and X-ray High Spatial-Resolution Microspectroscopy Measurements of Multistep Organic Transformation in Flow Microreactor Catalyzed by Au Nanoclusters
journal, February 2014

  • Gross, Elad; Shu, Xing-Zhong; Alayoglu, Selim
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja412740p

Nano-Chemical Infrared Imaging of Membrane Proteins in Lipid Bilayers
journal, November 2013

  • Berweger, Samuel; Nguyen, Duc M.; Muller, Eric A.
  • Journal of the American Chemical Society, Vol. 135, Issue 49
  • DOI: 10.1021/ja409815g

Infrared Chemical Nano-Imaging: Accessing Structure, Coupling, and Dynamics on Molecular Length Scales
journal, March 2015

  • Muller, Eric A.; Pollard, Benjamin; Raschke, Markus B.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00108

Easily Accessible Chiral Imidazolinium Salts Bearing Two Hydroxy-Containing Substituents as Shift Reagents and Carbene Precursors
journal, November 2006

  • Jurčík, Václav; Gilani, Mazhar; Wilhelm, René
  • European Journal of Organic Chemistry, Vol. 2006, Issue 22
  • DOI: 10.1002/ejoc.200600584

Modular Bidentate Hybrid NHC-Thioether Ligands for the Stabilization of Palladium Nanoparticles in Various Solvents
journal, April 2016

  • Rühling, Andreas; Schaepe, Kira; Rakers, Lena
  • Angewandte Chemie International Edition, Vol. 55, Issue 19
  • DOI: 10.1002/anie.201508933

Separation of Time-Resolved Phenomena in Surface-Enhanced Raman Scattering of the Photocatalytic Reduction of p -Nitrothiophenol
journal, December 2014

  • van Schrojenstein Lantman, E. M.; de Peinder, P.; Mank, A. J. G.
  • ChemPhysChem, Vol. 16, Issue 3
  • DOI: 10.1002/cphc.201402709

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming
journal, April 2015

  • Ristanović, Zoran; Hofmann, Jan P.; De Cremer, Gert
  • Journal of the American Chemical Society, Vol. 137, Issue 20
  • DOI: 10.1021/jacs.5b01698

    Works referencing / citing this record:

    Coumaraz-2-on-4-ylidene: Ambiphilic N-Heterocyclic Carbenes with a Tunable Electronic Structure
    journal, June 2018

    • Song, Hayoung; Kim, Hyunho; Lee, Eunsung
    • Angewandte Chemie International Edition, Vol. 57, Issue 28
    • DOI: 10.1002/anie.201804249

    Super-resolution imaging of non-fluorescent reactions via competition
    journal, July 2019


    Nanoscale chemical imaging using tip-enhanced Raman spectroscopy
    journal, March 2019


    In situ three-dimensional imaging of strain in gold nanocrystals during catalytic oxidation
    journal, January 2019

    • Suzana, Ana Flavia; Rochet, Amélie; Passos, Aline Ribeiro
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00231f

    Coumaraz-2-on-4-ylidene: Ambiphilic N-Heterocyclic Carbenes with a Tunable Electronic Structure
    journal, June 2018


    Super-resolution imaging of non-fluorescent reactions via competition
    journal, July 2019


    Nanoscale chemical imaging using tip-enhanced Raman spectroscopy
    journal, March 2019


    In situ three-dimensional imaging of strain in gold nanocrystals during catalytic oxidation
    journal, January 2019

    • Suzana, Ana Flavia; Rochet, Amélie; Passos, Aline Ribeiro
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00231f