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Title: Catalysis in real time using x-ray lasers

Abstract

Here, 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(0 0 0 1), 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:
 [1];  [2];  [3];  [4];  [5];  [6];  [1];  [1];  [7];  [8];  [4];  [1]
  1. Stockholm Univ., Stockholm (Sweden)
  2. Chapman Univ., Orange, CA (United States)
  3. Stockholm Univ., Stockholm (Sweden); Swedish Radiation Safety, Stockholm (Sweden)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. CNR-IOM, Trieste (Italy)
  6. Deutsches Elektronen-Synchrotron (DESY) Photon Science, Hamburg (Germany)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  8. Deutsches Elektronen-Synchrotron (DESY) Photon Science, Hamburg (Germany); Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1347236
Alternate Identifier(s):
OSTI ID: 1349281; OSTI ID: 1372896
Grant/Contract Number:
AC02-76SF00515
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 675; Journal Issue: C; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Country of Publication:
United States
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. United States: 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. United States. 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., and Pettersson, L. G. M. Tue . "Catalysis in real time using x-ray lasers". United States. doi: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 = {Here, 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(0 0 0 1), 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 = {United States},
year = {Tue Feb 14 00:00:00 EST 2017},
month = {Tue Feb 14 00:00:00 EST 2017}
}

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

Citation Metrics:
Cited by: 6works
Citation information provided by
Web of Science

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  • Here, 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(0 0 0 1), 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 gasmore » 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.« less
  • 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 themore » 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.« less
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