Reactivity on the (110) Surface of Ceria

A GGA+U Study of Surface Reduction and the Adsorption of CO and NO2

David O. Scanlon, Natasha M. Galea, Benjamin J. Morgan, Graeme W. Watson

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

The geometries and electronic structures resulting from surface reduction, CO adsorption, and NO2 adsorption at the (110) surface of CeO2 have been calculated using density functional theory corrected for on-site Coulomb interactions, GGA+U. We report a novel electronic structure for the reduced surface, denoted the split vacancy, which is more stable than the previously reported simple vacancy with subsurface CeIII. Analysis of CO adsorption modes highlights the importance of the geometry of the CO molecule when in contact with the surface, with a tilted adsorption mode being most energetically favorable with the formation of a carbonate anion coupled with surface reduction. A new bidentate adsorption mode is observed for NO2 adsorption, accompanied by partial surface oxidation. These novel structures observed on reduction, CO adsorption, and NO2 adsorption are all energetically more stable than the previously reported structures. In all of the systems, it was found that the location of the CeIII ions did not have a strong effect on the energetics, although they were coupled to strong local distortions of the structure.

Original languageEnglish
Pages (from-to)11095-11103
JournalJournal of Physical Chemistry C
Volume113
Issue number25
DOIs
Publication statusPublished - 25 Jun 2009

Fingerprint

Cerium compounds
Carbon Monoxide
reactivity
Adsorption
adsorption
Vacancies
Electronic structure
electronic structure
Geometry
Carbonates
geometry
Coulomb interactions
Density functional theory
Anions
carbonates
Negative ions
Ions
density functional theory
anions
Oxidation

Cite this

Reactivity on the (110) Surface of Ceria : A GGA+U Study of Surface Reduction and the Adsorption of CO and NO2. / Scanlon, David O.; Galea, Natasha M.; Morgan, Benjamin J.; Watson, Graeme W.

In: Journal of Physical Chemistry C, Vol. 113, No. 25, 25.06.2009, p. 11095-11103.

Research output: Contribution to journalArticle

Scanlon, David O. ; Galea, Natasha M. ; Morgan, Benjamin J. ; Watson, Graeme W. / Reactivity on the (110) Surface of Ceria : A GGA+U Study of Surface Reduction and the Adsorption of CO and NO2. In: Journal of Physical Chemistry C. 2009 ; Vol. 113, No. 25. pp. 11095-11103.
@article{a880c737b4fc4249bdb80ec915e0ef0c,
title = "Reactivity on the (110) Surface of Ceria: A GGA+U Study of Surface Reduction and the Adsorption of CO and NO2",
abstract = "The geometries and electronic structures resulting from surface reduction, CO adsorption, and NO2 adsorption at the (110) surface of CeO2 have been calculated using density functional theory corrected for on-site Coulomb interactions, GGA+U. We report a novel electronic structure for the reduced surface, denoted the split vacancy, which is more stable than the previously reported simple vacancy with subsurface CeIII. Analysis of CO adsorption modes highlights the importance of the geometry of the CO molecule when in contact with the surface, with a tilted adsorption mode being most energetically favorable with the formation of a carbonate anion coupled with surface reduction. A new bidentate adsorption mode is observed for NO2 adsorption, accompanied by partial surface oxidation. These novel structures observed on reduction, CO adsorption, and NO2 adsorption are all energetically more stable than the previously reported structures. In all of the systems, it was found that the location of the CeIII ions did not have a strong effect on the energetics, although they were coupled to strong local distortions of the structure.",
author = "Scanlon, {David O.} and Galea, {Natasha M.} and Morgan, {Benjamin J.} and Watson, {Graeme W.}",
year = "2009",
month = "6",
day = "25",
doi = "10.1021/jp9021085",
language = "English",
volume = "113",
pages = "11095--11103",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Reactivity on the (110) Surface of Ceria

T2 - A GGA+U Study of Surface Reduction and the Adsorption of CO and NO2

AU - Scanlon, David O.

AU - Galea, Natasha M.

AU - Morgan, Benjamin J.

AU - Watson, Graeme W.

PY - 2009/6/25

Y1 - 2009/6/25

N2 - The geometries and electronic structures resulting from surface reduction, CO adsorption, and NO2 adsorption at the (110) surface of CeO2 have been calculated using density functional theory corrected for on-site Coulomb interactions, GGA+U. We report a novel electronic structure for the reduced surface, denoted the split vacancy, which is more stable than the previously reported simple vacancy with subsurface CeIII. Analysis of CO adsorption modes highlights the importance of the geometry of the CO molecule when in contact with the surface, with a tilted adsorption mode being most energetically favorable with the formation of a carbonate anion coupled with surface reduction. A new bidentate adsorption mode is observed for NO2 adsorption, accompanied by partial surface oxidation. These novel structures observed on reduction, CO adsorption, and NO2 adsorption are all energetically more stable than the previously reported structures. In all of the systems, it was found that the location of the CeIII ions did not have a strong effect on the energetics, although they were coupled to strong local distortions of the structure.

AB - The geometries and electronic structures resulting from surface reduction, CO adsorption, and NO2 adsorption at the (110) surface of CeO2 have been calculated using density functional theory corrected for on-site Coulomb interactions, GGA+U. We report a novel electronic structure for the reduced surface, denoted the split vacancy, which is more stable than the previously reported simple vacancy with subsurface CeIII. Analysis of CO adsorption modes highlights the importance of the geometry of the CO molecule when in contact with the surface, with a tilted adsorption mode being most energetically favorable with the formation of a carbonate anion coupled with surface reduction. A new bidentate adsorption mode is observed for NO2 adsorption, accompanied by partial surface oxidation. These novel structures observed on reduction, CO adsorption, and NO2 adsorption are all energetically more stable than the previously reported structures. In all of the systems, it was found that the location of the CeIII ions did not have a strong effect on the energetics, although they were coupled to strong local distortions of the structure.

UR - http://dx.doi.org/10.1021/jp9021085

U2 - 10.1021/jp9021085

DO - 10.1021/jp9021085

M3 - Article

VL - 113

SP - 11095

EP - 11103

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 25

ER -