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Title: OH Group Dynamics of 1,3-Propanediol on TiO 2 (110)

Abstract

Variable-temperature scanning tunneling microscopy and dispersion-corrected density functional theory were employed to study the interaction of 1,3 propanediol with reduced TiO2(110) surfaces. We find that at 300 K, 1,3-propanediol molecules dissociate via O-H bond scission of one of the OH groups on bridge-bonded oxygen (Ob) vacancy (VO) defects forming pairs of monoalkoxide (Ob-(CH2)3-OH) and bridge-bonded bonded hydroxyl (HOb) species. The OH group of the monoalkoxide species is bound to the adjacent 5-coordinated Ti4+ (Ti5c) sites. The Ob-(CH2)3-OH species are observed to rotate around their Ob anchor, switching the position of the OH between the two adjacent Ti5c rows. The rotating species are found to assist the cross-Ob row HOb hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming bidentate type dioxo (Ob-(CH2)3-"O" _("Ti" _"5c" )) species and an additional HOb. The reversible interconversion between the mono- and di-oxo species illustrates a formation of the equilibrium between these conjugate acid/base pairs.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1064596
Report Number(s):
PNNL-SA-90595
Journal ID: ISSN 1948-7185; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 3; Journal Issue: 22; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Zhenrong, Yoon, Yeohoon, Lin, Xiao, Acharya, Danda, Kay, Bruce D., Rousseau, Roger, and Dohnálek, Zdenek. OH Group Dynamics of 1,3-Propanediol on TiO 2 (110). United States: N. p., 2012. Web. doi:10.1021/jz301412m.
Zhang, Zhenrong, Yoon, Yeohoon, Lin, Xiao, Acharya, Danda, Kay, Bruce D., Rousseau, Roger, & Dohnálek, Zdenek. OH Group Dynamics of 1,3-Propanediol on TiO 2 (110). United States. doi:10.1021/jz301412m.
Zhang, Zhenrong, Yoon, Yeohoon, Lin, Xiao, Acharya, Danda, Kay, Bruce D., Rousseau, Roger, and Dohnálek, Zdenek. Thu . "OH Group Dynamics of 1,3-Propanediol on TiO 2 (110)". United States. doi:10.1021/jz301412m.
@article{osti_1064596,
title = {OH Group Dynamics of 1,3-Propanediol on TiO 2 (110)},
author = {Zhang, Zhenrong and Yoon, Yeohoon and Lin, Xiao and Acharya, Danda and Kay, Bruce D. and Rousseau, Roger and Dohnálek, Zdenek},
abstractNote = {Variable-temperature scanning tunneling microscopy and dispersion-corrected density functional theory were employed to study the interaction of 1,3 propanediol with reduced TiO2(110) surfaces. We find that at 300 K, 1,3-propanediol molecules dissociate via O-H bond scission of one of the OH groups on bridge-bonded oxygen (Ob) vacancy (VO) defects forming pairs of monoalkoxide (Ob-(CH2)3-OH) and bridge-bonded bonded hydroxyl (HOb) species. The OH group of the monoalkoxide species is bound to the adjacent 5-coordinated Ti4+ (Ti5c) sites. The Ob-(CH2)3-OH species are observed to rotate around their Ob anchor, switching the position of the OH between the two adjacent Ti5c rows. The rotating species are found to assist the cross-Ob row HOb hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming bidentate type dioxo (Ob-(CH2)3-"O" _("Ti" _"5c" )) species and an additional HOb. The reversible interconversion between the mono- and di-oxo species illustrates a formation of the equilibrium between these conjugate acid/base pairs.},
doi = {10.1021/jz301412m},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 22,
volume = 3,
place = {United States},
year = {2012},
month = {11}
}