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Title: Structure and Dynamics of CO 2 on Rutile TiO 2 (110)-1×1

Abstract

Adsorption, binding, and diffusion of CO2 molecules on rutile TiO2(110) model surfaces was investigated experimentally using scanning tunneling microscopy, infrared reflection adsorption spectroscopy (IRAS), 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 is stabilized by CO2 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 chainsmore » 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 due to quadrupole-quadrupole interactions with the Ti5c-bound CO2 molecules.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Fundamental and Computational Sciences Directorate, §Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1059191
Report Number(s):
PNNL-SA-89052
Journal ID: ISSN 1932-7447; 46005; 40077; 39940; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 50; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

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, and Dohnálek, Zdenek. Structure and Dynamics of CO2 on Rutile TiO2 (110)-1×1. United States: N. p., 2012. Web. doi:10.1021/jp308061j.
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. United States. doi:10.1021/jp308061j.
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, and Dohnálek, Zdenek. Tue . "Structure and Dynamics of CO2 on Rutile TiO2 (110)-1×1". United States. doi:10.1021/jp308061j.
@article{osti_1059191,
title = {Structure and Dynamics of CO2 on Rutile TiO2 (110)-1×1},
author = {Lin, Xiao and Yoon, Yeohoon and Petrik, Nikolay G. and Li, Zhenjun and Wang, Zhi-Tao and Glezakou, Vassiliki-Alexandra and Kay, Bruce D. and Lyubinetsky, Igor and Kimmel, Greg A. and Rousseau, Roger and Dohnálek, Zdenek},
abstractNote = {Adsorption, binding, and diffusion of CO2 molecules on rutile TiO2(110) model surfaces was investigated experimentally using scanning tunneling microscopy, infrared reflection adsorption spectroscopy (IRAS), 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 is stabilized by CO2 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 due to quadrupole-quadrupole interactions with the Ti5c-bound CO2 molecules.},
doi = {10.1021/jp308061j},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 50,
volume = 116,
place = {United States},
year = {2012},
month = {10}
}