DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Catalysis in real time using X-ray lasers

Abstract

We describe how the unique temporal and spectral characteristics of X-ray free-electron lasers (XFEL) can be utilized to follow chemical transformations in heterogeneous catalysis in real time. We highlight the systematic study of CO oxidation on Ru(0001), which we initiate either using a femtosecond pulse from an optical laser or by activating only the oxygen atoms using a THz pulse. We find that CO is promoted into an entropy-controlled precursor state prior to desorbing when the surface is heated in the absence of oxygen, whereas in the presence of oxygen, CO desorbs directly into the gas phase. We monitor the activation of atomic oxygen explicitly by the reduced split between bonding and antibonding orbitals as the oxygen comes out of the strongly bound hollow position. Applying these novel XFEL techniques to the full oxidation reaction resulted in the surprising observation of a significant fraction of the reactants at the transition state through the electronic signature of the new bond formation.

Authors:
; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1347236
Alternate Identifier(s):
OSTI ID: 1349281; OSTI ID: 1372896
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Name: Chemical Physics Letters Journal Volume: 675 Journal Issue: C; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY

Citation Formats

Nilsson, A., LaRue, J., Öberg, H., Ogasawara, H., Dell'Angela, M., Beye, M., Öström, H., Gladh, J., Nørskov, J. K., Wurth, W., Abild-Pedersen, F., and Pettersson, L. G. M. Catalysis in real time using X-ray lasers. Netherlands: N. p., 2017. Web. doi:10.1016/j.cplett.2017.02.018.
Nilsson, A., LaRue, J., Öberg, H., Ogasawara, H., Dell'Angela, M., Beye, M., Öström, H., Gladh, J., Nørskov, J. K., Wurth, W., Abild-Pedersen, F., & Pettersson, L. G. M. Catalysis in real time using X-ray lasers. Netherlands. https://doi.org/10.1016/j.cplett.2017.02.018
Nilsson, A., LaRue, J., Öberg, H., Ogasawara, H., Dell'Angela, M., Beye, M., Öström, H., Gladh, J., Nørskov, J. K., Wurth, W., Abild-Pedersen, F., and Pettersson, L. G. M. Mon . "Catalysis in real time using X-ray lasers". Netherlands. https://doi.org/10.1016/j.cplett.2017.02.018.
@article{osti_1347236,
title = {Catalysis in real time using X-ray lasers},
author = {Nilsson, A. and LaRue, J. and Öberg, H. and Ogasawara, H. and Dell'Angela, M. and Beye, M. and Öström, H. and Gladh, J. and Nørskov, J. K. and Wurth, W. and Abild-Pedersen, F. and Pettersson, L. G. M.},
abstractNote = {We describe how the unique temporal and spectral characteristics of X-ray free-electron lasers (XFEL) can be utilized to follow chemical transformations in heterogeneous catalysis in real time. We highlight the systematic study of CO oxidation on Ru(0001), which we initiate either using a femtosecond pulse from an optical laser or by activating only the oxygen atoms using a THz pulse. We find that CO is promoted into an entropy-controlled precursor state prior to desorbing when the surface is heated in the absence of oxygen, whereas in the presence of oxygen, CO desorbs directly into the gas phase. We monitor the activation of atomic oxygen explicitly by the reduced split between bonding and antibonding orbitals as the oxygen comes out of the strongly bound hollow position. Applying these novel XFEL techniques to the full oxidation reaction resulted in the surprising observation of a significant fraction of the reactants at the transition state through the electronic signature of the new bond formation.},
doi = {10.1016/j.cplett.2017.02.018},
journal = {Chemical Physics Letters},
number = C,
volume = 675,
place = {Netherlands},
year = {Mon May 01 00:00:00 EDT 2017},
month = {Mon May 01 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.cplett.2017.02.018

Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Catalytic CO Oxidation by O 2 Mediated by Noble-Metal-Free Cluster Anions Cu 2 VO 3 - 5
journal, February 2018


Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox-System [AlVO x ] +. /CO/N 2 O ( x= 3, 4) durch Gasphasen-Infrarotspektroskopie
journal, May 2018

  • Debnath, Sreekanta; Knorke, Harald; Schöllkopf, Wieland
  • Angewandte Chemie, Vol. 130, Issue 25
  • DOI: 10.1002/ange.201804056

Experimental Identification of the Active Site in the Heteronuclear Redox Couples [AlVO x ] +. /CO/N 2 O ( x= 3, 4) by Gas-Phase IR Spectroscopy
journal, May 2018

  • Debnath, Sreekanta; Knorke, Harald; Schöllkopf, Wieland
  • Angewandte Chemie International Edition, Vol. 57, Issue 25
  • DOI: 10.1002/anie.201804056

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy
journal, January 2019

  • Schwarz, Helmut; Asmis, Knut R.
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201805836

Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction
journal, January 2018


Picosecond timescale tracking of pentacene triplet excitons with chemical sensitivity
journal, June 2019


Perspective: Opportunities for ultrafast science at SwissFEL
journal, November 2017

  • Abela, Rafael; Beaud, Paul; van Bokhoven, Jeroen A.
  • Structural Dynamics, Vol. 4, Issue 6
  • DOI: 10.1063/1.4997222

Atom-specific activation in CO oxidation
journal, December 2018

  • Schreck, Simon; Diesen, Elias; LaRue, Jerry
  • The Journal of Chemical Physics, Vol. 149, Issue 23
  • DOI: 10.1063/1.5044579

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers
journal, April 2019

  • Wernet, Philippe
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
  • DOI: 10.1098/rsta.2017.0464

Short-wavelength free-electron laser sources and science: a review
text, January 2017

  • Seddon, E. A.; Clarke, J. A.; Dunning, D. J.
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2018-00596