A density functional theory study of formaldehyde adsorption on ceria

Donghai Mei, N. Aaron Deskins, Michel Dupuis

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Molecular adsorption of formaldehyde on the stoichiometric CeO2(1 1 1) and CeO2(1 1 0) surfaces was studied using periodic density functional theory. Two adsorption modes (strong chemisorbed and weak physisorbed) were identified on both surfaces. This is consistent with recent experimental observations. On the (1 1 1) surface, formaldehyde strongly chemisorbs with an adsorption energy of 0.86 eV to form a dioxymethylene-like structure, in which a surface O lifts from the surface to bind with the C of formaldehyde. A weak physisorbed state with adsorption energy of 0.28 eV was found with the O of formaldehyde interacting with a surface Ce. On the (1 1 0) surface, dioxymethyelene formation was also observed, with an adsorption energy of 1.31 eV. The weakly adsorbed state of formaldehyde on the (1 1 0) surface was energetically comparable to the weak adsorption state on the (1 1 1) surface. Analysis of the local density of states and charge density differences after adsorption shows that strong covalent bonding occurs between the C of formaldehyde and surface O when dioxymethylene forms. Calculated vibrational frequencies also confirm dioxymethylene formation. Our results show that as the coverage increases, the adsorption of formaldehyde on the (1 1 1) surface becomes weak, but is nearly unaffected on the (1 1 0) surface.

Original languageEnglish
Pages (from-to)4993-5001
Number of pages9
JournalSurface Science
Volume601
Issue number21
DOIs
Publication statusPublished - Nov 1 2007

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Cerium compounds
formaldehyde
Formaldehyde
Density functional theory
density functional theory
Adsorption
adsorption
Vibrational spectra
Charge density
energy

Keywords

  • Adsorption
  • Cerium dioxide
  • Density functional calculations
  • Formaldehyde
  • Stoichiometric
  • Surfaces

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces

Cite this

A density functional theory study of formaldehyde adsorption on ceria. / Mei, Donghai; Aaron Deskins, N.; Dupuis, Michel.

In: Surface Science, Vol. 601, No. 21, 01.11.2007, p. 4993-5001.

Research output: Contribution to journalArticle

Mei, Donghai ; Aaron Deskins, N. ; Dupuis, Michel. / A density functional theory study of formaldehyde adsorption on ceria. In: Surface Science. 2007 ; Vol. 601, No. 21. pp. 4993-5001.
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