OH group dynamics of 1,3-propanediol on TiO2(110)

Zhenrong Zhang; Yeohoon Yoon; Xiao Lin; Danda Acharya; Bruce D. Kay; Roger Rousseau; Zdenek Dohnálek

doi:10.1021/jz301412m

OH group dynamics of 1,3-propanediol on TiO₂(110)

Zhenrong Zhang, Yeohoon Yoon, Xiao Lin, Danda Acharya, Bruce D. Kay, Roger Rousseau, Zdenek Dohnálek

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

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 (O_b) vacancy (V_O) defects forming pairs of monoalkoxide (O_b-(CH₂)₃-OH) and bridge-bonded bonded hydroxyl (HO_b) species. The OH group of the monoalkoxide species is bound to the adjacent 5-coordinated Ti⁴⁺ (Ti_5c) sites. The O_b-(CH₂)₃-OH species are observed to rotate around their O_b anchor, switching the position of the OH between the two adjacent Ti_5c rows. The rotating species are found to assist cross-O_b row HO_b hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming a bidentate type dioxo (O_b-(CH₂) ₃-O_Ti5c) species and an additional HO_b. The reversible interconversion between the mono and dioxo species illustrates the attainment of a dynamic equilibrium between these conjugate acid/base pairs.

Original language	English
Pages (from-to)	3257-3263
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	3
Issue number	22
DOIs	https://doi.org/10.1021/jz301412m
State	Published - Nov 15 2012
Externally published	Yes

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title = "OH group dynamics of 1,3-propanediol on TiO2(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 cross-Ob row HOb hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming a bidentate type dioxo (Ob-(CH2) 3-OTi5c) species and an additional HOb. The reversible interconversion between the mono and dioxo species illustrates the attainment of a dynamic equilibrium between these conjugate acid/base pairs.",

author = "Zhenrong Zhang and Yeohoon Yoon and Xiao Lin and Danda Acharya and Kay, {Bruce D.} and Roger Rousseau and Zdenek Dohn{\'a}lek",

year = "2012",

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doi = "10.1021/jz301412m",

language = "English",

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journal = "Journal of Physical Chemistry Letters",

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T1 - OH group dynamics of 1,3-propanediol on TiO2(110)

AU - Zhang, Zhenrong

AU - Yoon, Yeohoon

AU - Lin, Xiao

AU - Acharya, Danda

AU - Kay, Bruce D.

AU - Rousseau, Roger

AU - Dohnálek, Zdenek

PY - 2012/11/15

Y1 - 2012/11/15

N2 - 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 cross-Ob row HOb hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming a bidentate type dioxo (Ob-(CH2) 3-OTi5c) species and an additional HOb. The reversible interconversion between the mono and dioxo species illustrates the attainment of a dynamic equilibrium between these conjugate acid/base pairs.

AB - 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 cross-Ob row HOb hydrogen transfer. The OH group of the monoalkoxide species is further observed to dissociate forming a bidentate type dioxo (Ob-(CH2) 3-OTi5c) species and an additional HOb. The reversible interconversion between the mono and dioxo species illustrates the attainment of a dynamic equilibrium between these conjugate acid/base pairs.

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DO - 10.1021/jz301412m

M3 - Article

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SN - 1948-7185

VL - 3

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EP - 3263

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 22

ER -

OH group dynamics of 1,3-propanediol on TiO₂(110)

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