Structure and dynamics of CO2 on rutile TiO2 (110)-1×1

Xiao Lin, Yeohoon Yoon, Nikolay G. Petrik, Zhenjun Li, Zhi Tao Wang, Vassiliki Alexandra Glezakou, Bruce D. Kay, Igor Lyubinetsky, Greg A. Kimmel, Roger Rousseau, Zdenek Dohnálek

Research output: Contribution to journalArticle

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Abstract

Adsorption, binding, and diffusion of CO2 molecules on model rutile TiO2 (110)-1×1 surfaces were investigated experimentally using scanning tunneling microscopy, infrared reflection adsorption spectroscopy (IRAS), molecular beam scattering, and temperature programmed desorption and theoretically via dispersion corrected density functional theory and ab initio molecular dynamics. In accord with previous studies, bridging oxygen (Ob) vacancies (VO's) are found to be the most stable binding sites. Additional CO2 adsorbs on 5-coordinated Ti sites (Ti5c) with the initial small fraction stabilized by CO2 adsorbed on VO sites. The Ti5c-bound CO2 is found to be highly mobile at 50 K at coverages of up to 1/2 monolayer (ML). Theoretical studies show that the CO2 diffusion on Ti5c rows proceeds via a rotation-tumbling mechanism with extremely low barrier of 0.06 eV. The Ti5c-bound CO2 molecules are found to bind preferentially to a single Ti5c with the O=C=O axis tilted away from the surface normal. The binding energy of tilted CO2 molecules changes only slightly with changes in the azimuth of the CO2 tilt angle. At 2/3 ML, CO2 diffusion is hindered and at 1 ML an ordered (2×2) overlayer with a zigzag arrangement of tilted CO2 molecules develops along the Ti5c rows. Out of phase arrangement of the zigzag chains is observed across the rows. An additional 0.5 ML of CO2 can be adsorbed at Ob sites with a binding energy only slightly lower than that on Ti5c sites presumably due to quadrupole-quadrupole interactions with the Ti5c-bound CO2 molecules.

Original languageEnglish
Pages (from-to)26625-26635
Number of pages11
JournalJournal of Physical Chemistry C
Volume116
Issue number50
DOIs
Publication statusPublished - Dec 20 2012

Fingerprint

rutile
Monolayers
Molecules
molecules
Binding energy
quadrupoles
binding energy
Adsorption
Barreling
adsorption
Molecular beams
infrared reflection
Scanning tunneling microscopy
Binding sites
Oxygen vacancies
Temperature programmed desorption
azimuth
molecular beams
Density functional theory
Molecular dynamics

ASJC Scopus subject areas

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

Cite this

Lin, X., Yoon, Y., Petrik, N. G., Li, Z., Wang, Z. T., Glezakou, V. A., ... Dohnálek, Z. (2012). Structure and dynamics of CO2 on rutile TiO2 (110)-1×1. Journal of Physical Chemistry C, 116(50), 26625-26635. https://doi.org/10.1021/jp308849t

Structure and dynamics of CO2 on rutile TiO2 (110)-1×1. / Lin, Xiao; Yoon, Yeohoon; Petrik, Nikolay G.; Li, Zhenjun; Wang, Zhi Tao; Glezakou, Vassiliki Alexandra; Kay, Bruce D.; Lyubinetsky, Igor; Kimmel, Greg A.; Rousseau, Roger; Dohnálek, Zdenek.

In: Journal of Physical Chemistry C, Vol. 116, No. 50, 20.12.2012, p. 26625-26635.

Research output: Contribution to journalArticle

Lin, X, Yoon, Y, Petrik, NG, Li, Z, Wang, ZT, Glezakou, VA, Kay, BD, Lyubinetsky, I, Kimmel, GA, Rousseau, R & Dohnálek, Z 2012, 'Structure and dynamics of CO2 on rutile TiO2 (110)-1×1', Journal of Physical Chemistry C, vol. 116, no. 50, pp. 26625-26635. https://doi.org/10.1021/jp308849t
Lin X, Yoon Y, Petrik NG, Li Z, Wang ZT, Glezakou VA et al. Structure and dynamics of CO2 on rutile TiO2 (110)-1×1. Journal of Physical Chemistry C. 2012 Dec 20;116(50):26625-26635. https://doi.org/10.1021/jp308849t
Lin, Xiao ; Yoon, Yeohoon ; Petrik, Nikolay G. ; Li, Zhenjun ; Wang, Zhi Tao ; Glezakou, Vassiliki Alexandra ; Kay, Bruce D. ; Lyubinetsky, Igor ; Kimmel, Greg A. ; Rousseau, Roger ; Dohnálek, Zdenek. / Structure and dynamics of CO2 on rutile TiO2 (110)-1×1. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 50. pp. 26625-26635.
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