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Hydrogen-Promoted Chlorination of RuO2(110)

Hofmann, Jan Philipp; Zweidinger, Stefan; Knapp, Marcus; Seitsonen, Ari Paavo; Schulte, Karina LU ; Andersen, Jesper N LU ; Lundgren, Edvin LU and Over, Herbert (2010) In Journal of Physical Chemistry C 114(24). p.10901-10909
Abstract
High-resolution core-level photoemission spectroscopy and temperature-programmed reaction experiments together with density functional theory calculations were used to elucidate on the atomic scale the chlorination mechanism of ruthenium dioxide RuO2(110) by hydrogen chloride exposure. The surface-selective chlorination accounts for the extraordinary stability of the RuO2 catalyst in the Sumitomo process-the heterogeneously catalyzed oxidation of hydrogen chloride by oxygen. The selective replacement of bridging oxygen atoms by chlorine atoms depends on the formation of water molecules serving as leaving groups. Water is produced by the chlorine-assisted recombination of two neighboring surface hydroxyl groups at around 450 K, a... (More)
High-resolution core-level photoemission spectroscopy and temperature-programmed reaction experiments together with density functional theory calculations were used to elucidate on the atomic scale the chlorination mechanism of ruthenium dioxide RuO2(110) by hydrogen chloride exposure. The surface-selective chlorination accounts for the extraordinary stability of the RuO2 catalyst in the Sumitomo process-the heterogeneously catalyzed oxidation of hydrogen chloride by oxygen. The selective replacement of bridging oxygen atoms by chlorine atoms depends on the formation of water molecules serving as leaving groups. Water is produced by the chlorine-assisted recombination of two neighboring surface hydroxyl groups at around 450 K, a temperature where water instantaneously leaves the surface. Finally, the bridging vacancy is rapidly filled in by chlorine atoms, thereby forming bridging chlorine atoms. Preadsorbed hydrogen has shown to facilitate the chlorination process for stoichiometry reasons. The general strategy of transforming bridging O atoms into a good leaving group has been corroborated by the chlorination of RuO2(110) via CO pretreatment with CO2 as the leaving group and subsequent Cl-2 exposure. (Less)
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organization
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type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
114
issue
24
pages
10901 - 10909
publisher
The American Chemical Society
external identifiers
  • wos:000278845300032
  • scopus:77953790577
ISSN
1932-7447
DOI
10.1021/jp103199x
language
English
LU publication?
yes
id
6f35036a-125c-43b0-863d-85e8715ef389 (old id 1630394)
date added to LUP
2010-07-22 14:26:35
date last changed
2018-05-29 09:35:19
@article{6f35036a-125c-43b0-863d-85e8715ef389,
  abstract     = {High-resolution core-level photoemission spectroscopy and temperature-programmed reaction experiments together with density functional theory calculations were used to elucidate on the atomic scale the chlorination mechanism of ruthenium dioxide RuO2(110) by hydrogen chloride exposure. The surface-selective chlorination accounts for the extraordinary stability of the RuO2 catalyst in the Sumitomo process-the heterogeneously catalyzed oxidation of hydrogen chloride by oxygen. The selective replacement of bridging oxygen atoms by chlorine atoms depends on the formation of water molecules serving as leaving groups. Water is produced by the chlorine-assisted recombination of two neighboring surface hydroxyl groups at around 450 K, a temperature where water instantaneously leaves the surface. Finally, the bridging vacancy is rapidly filled in by chlorine atoms, thereby forming bridging chlorine atoms. Preadsorbed hydrogen has shown to facilitate the chlorination process for stoichiometry reasons. The general strategy of transforming bridging O atoms into a good leaving group has been corroborated by the chlorination of RuO2(110) via CO pretreatment with CO2 as the leaving group and subsequent Cl-2 exposure.},
  author       = {Hofmann, Jan Philipp and Zweidinger, Stefan and Knapp, Marcus and Seitsonen, Ari Paavo and Schulte, Karina and Andersen, Jesper N and Lundgren, Edvin and Over, Herbert},
  issn         = {1932-7447},
  language     = {eng},
  number       = {24},
  pages        = {10901--10909},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry C},
  title        = {Hydrogen-Promoted Chlorination of RuO2(110)},
  url          = {http://dx.doi.org/10.1021/jp103199x},
  volume       = {114},
  year         = {2010},
}