Theoretical Study of Trimethylacetic Acid Adsorption on CeO2(111) Surface

Weina Wang, S. Thevuthasan, Wenliang Wang, Ping Yang

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces was investigated using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA- + H+) were identified on stoichiometric and oxygen-deficient CeO2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states. The most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce-O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.

Original languageEnglish
Pages (from-to)2655-2666
Number of pages12
JournalJournal of Physical Chemistry C
Volume120
Issue number5
DOIs
Publication statusPublished - 18 Feb 2016
Externally publishedYes

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Adsorption
acids
adsorption
Acids
oxygen
Oxygen
Surface states
Vibrational spectra
Oxygen vacancies
configurations
Coulomb interactions
Discrete Fourier transforms
Electronic structure
Density functional theory
energy
signatures
interactions
density functional theory
electronic structure
Molecules

ASJC Scopus subject areas

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

Cite this

Theoretical Study of Trimethylacetic Acid Adsorption on CeO2(111) Surface. / Wang, Weina; Thevuthasan, S.; Wang, Wenliang; Yang, Ping.

In: Journal of Physical Chemistry C, Vol. 120, No. 5, 18.02.2016, p. 2655-2666.

Research output: Contribution to journalArticle

Wang, Weina ; Thevuthasan, S. ; Wang, Wenliang ; Yang, Ping. / Theoretical Study of Trimethylacetic Acid Adsorption on CeO2(111) Surface. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 5. pp. 2655-2666.
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