Methanol adsorption on the clean CeO 2(111) saurface: A density functional theory study

Donghai Mei, N. Aaron Deskins, Michel Dupuis, Qingfeng Ge

Research output: Contribution to journalArticle

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Abstract

Molecular and dissociative adsorption of methanol at various sites on the stoichiometric CeO 2(111) surface have been studied using density functional theory periodic calculations. At 0.25 monolayer (ML) coverage, the dissociative adsorption with an adsorption energy of 0.55 eV is slightly favored. The most stable state is the dissociative adsorption of methanol via C-H bond breaking, forming a coadsorbed hydroxymethyl group and hydrogen adatom on two separate O 3C surface sites. The strongest molecular adsorption occurs through an O-Ce 7c connection with an adsorption energy of 0.48 eV. At methanol coverage of 0.5 ML, the dissociative adsorption and the molecular adsorption became competitive. The adsorption energy per methanol molecule for both adsorption modes falls into a narrow range of 0.46-0.55 eV. As methanol coverage increases beyond 0.5 ML, the molecular adsorption becomes more energetically favorable than the dissociative adsorption because of the attractive hydrogen bonding between coadsorbed methanol molecules. At full monolayer, the adsorption energy of molecular adsorption is 0.40 eV per molecule while the adsorption energy for total dissociative adsorption of methanol is only 0.17 eV. The results at different methanol coverages indicate that methanol can adsorb on a defect-free CeO 2(111) surface, which are also consistent with experimental observations.

Original languageEnglish
Pages (from-to)10514-10522
Number of pages9
JournalJournal of Physical Chemistry C
Volume111
Issue number28
DOIs
Publication statusPublished - Jul 19 2007

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Density functional theory
Methanol
methyl alcohol
density functional theory
Adsorption
adsorption
Monolayers
Molecules
energy
molecules
Adatoms
hydrogen
adatoms
Hydrogen
Hydrogen bonds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Methanol adsorption on the clean CeO 2(111) saurface : A density functional theory study. / Mei, Donghai; Aaron Deskins, N.; Dupuis, Michel; Ge, Qingfeng.

In: Journal of Physical Chemistry C, Vol. 111, No. 28, 19.07.2007, p. 10514-10522.

Research output: Contribution to journalArticle

Mei, Donghai ; Aaron Deskins, N. ; Dupuis, Michel ; Ge, Qingfeng. / Methanol adsorption on the clean CeO 2(111) saurface : A density functional theory study. In: Journal of Physical Chemistry C. 2007 ; Vol. 111, No. 28. pp. 10514-10522.
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