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

Journal Article · · Journal of Physical Chemistry Letters
DOI:https://doi.org/10.1021/jz301412m· OSTI ID:1064596

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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1064596
Report Number(s):
PNNL-SA-90595; KC0302010
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 22 Vol. 3; ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

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