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Adsorption and Dissociation of CO on Bare and Ni-Decorated Stepped Rh(553) Surfaces

Stroppa, A.; Mittendorfer, F.; Andersen, Jesper N LU ; Parteder, G.; Allegretti, F.; Surnev, S. and Netzer, F. P. (2009) In Journal of Physical Chemistry C 113(3). p.942-949
Abstract
The adsorption and dissociation of carbon monoxide were studied with plane-wave density functional theory on flat Rh(111), stepped and kinked Rh(553), and Ni-decorated Rh(553) surfaces. The theoretical results were compared to high-resolution X-ray photoelectron spectroscopy (HR-XPS) experiments. The most favorable CO adsorption sites for low coverages were identified by a systematic calculation of the adsorption energies, and their sequence of occupation as a function of CO exposure was determined experimentally in C 1s HR-XPS spectra via their characteristic surface core-level shifts. On the clean, stepped (553) surface, molecular CO is adsorbed more strongly on low-coordinated top sites at the step edge, but on the Ni-decorated surface,... (More)
The adsorption and dissociation of carbon monoxide were studied with plane-wave density functional theory on flat Rh(111), stepped and kinked Rh(553), and Ni-decorated Rh(553) surfaces. The theoretical results were compared to high-resolution X-ray photoelectron spectroscopy (HR-XPS) experiments. The most favorable CO adsorption sites for low coverages were identified by a systematic calculation of the adsorption energies, and their sequence of occupation as a function of CO exposure was determined experimentally in C 1s HR-XPS spectra via their characteristic surface core-level shifts. On the clean, stepped (553) surface, molecular CO is adsorbed more strongly on low-coordinated top sites at the step edge, but on the Ni-decorated surface, the binding is stronger at the terrace sites. The barrier for dissociation with respect to the gas phase is about 1 eV lower on the stepped Rh(553) surface than on the flat Rh(111) surface, implying a substantially higher reaction rate. The presence of kinks at the clean Rh(553) surface does not lead to a significant additional decrease of the dissociation barriers, resulting in dissociation energies just above the desorption threshold for both stepped and kinked surfaces, whereas the barrier can be additionally lowered by about 0.1 eV by decorating the step edges with Ni stripes. Whereas no dissociation of CO was observed by HR-XPS on the clean Rh(553) surface, a minor amount of CO dissociation was found on the Ni-decorated Rh surface, in agreement with the theoretical predictions. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
113
issue
3
pages
942 - 949
publisher
The American Chemical Society
external identifiers
  • wos:000262522000023
  • scopus:61649098164
ISSN
1932-7447
DOI
10.1021/jp806424t
language
English
LU publication?
yes
id
a3db373a-9ea0-4c2c-b41f-05b592c71238 (old id 1312562)
date added to LUP
2009-03-13 13:48:04
date last changed
2017-07-09 03:33:32
@article{a3db373a-9ea0-4c2c-b41f-05b592c71238,
  abstract     = {The adsorption and dissociation of carbon monoxide were studied with plane-wave density functional theory on flat Rh(111), stepped and kinked Rh(553), and Ni-decorated Rh(553) surfaces. The theoretical results were compared to high-resolution X-ray photoelectron spectroscopy (HR-XPS) experiments. The most favorable CO adsorption sites for low coverages were identified by a systematic calculation of the adsorption energies, and their sequence of occupation as a function of CO exposure was determined experimentally in C 1s HR-XPS spectra via their characteristic surface core-level shifts. On the clean, stepped (553) surface, molecular CO is adsorbed more strongly on low-coordinated top sites at the step edge, but on the Ni-decorated surface, the binding is stronger at the terrace sites. The barrier for dissociation with respect to the gas phase is about 1 eV lower on the stepped Rh(553) surface than on the flat Rh(111) surface, implying a substantially higher reaction rate. The presence of kinks at the clean Rh(553) surface does not lead to a significant additional decrease of the dissociation barriers, resulting in dissociation energies just above the desorption threshold for both stepped and kinked surfaces, whereas the barrier can be additionally lowered by about 0.1 eV by decorating the step edges with Ni stripes. Whereas no dissociation of CO was observed by HR-XPS on the clean Rh(553) surface, a minor amount of CO dissociation was found on the Ni-decorated Rh surface, in agreement with the theoretical predictions.},
  author       = {Stroppa, A. and Mittendorfer, F. and Andersen, Jesper N and Parteder, G. and Allegretti, F. and Surnev, S. and Netzer, F. P.},
  issn         = {1932-7447},
  language     = {eng},
  number       = {3},
  pages        = {942--949},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry C},
  title        = {Adsorption and Dissociation of CO on Bare and Ni-Decorated Stepped Rh(553) Surfaces},
  url          = {http://dx.doi.org/10.1021/jp806424t},
  volume       = {113},
  year         = {2009},
}