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Title: Facet-specific interaction between methanol and TiO 2 probed by sum-frequency vibrational spectroscopy

Abstract

The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼−20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼−5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.

Authors:
; ; ; ; ORCiD logo; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1432428
Grant/Contract Number:  
AC03-76SF00098
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 17; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Yang, Deheng, Li, Yadong, Liu, Xinyi, Cao, Yue, Gao, Yi, Shen, Y. Ron, and Liu, Wei-Tao. Facet-specific interaction between methanol and TiO 2 probed by sum-frequency vibrational spectroscopy. United States: N. p., 2018. Web. doi:10.1073/pnas.1802741115.
Yang, Deheng, Li, Yadong, Liu, Xinyi, Cao, Yue, Gao, Yi, Shen, Y. Ron, & Liu, Wei-Tao. Facet-specific interaction between methanol and TiO 2 probed by sum-frequency vibrational spectroscopy. United States. doi:10.1073/pnas.1802741115.
Yang, Deheng, Li, Yadong, Liu, Xinyi, Cao, Yue, Gao, Yi, Shen, Y. Ron, and Liu, Wei-Tao. Mon . "Facet-specific interaction between methanol and TiO 2 probed by sum-frequency vibrational spectroscopy". United States. doi:10.1073/pnas.1802741115.
@article{osti_1432428,
title = {Facet-specific interaction between methanol and TiO 2 probed by sum-frequency vibrational spectroscopy},
author = {Yang, Deheng and Li, Yadong and Liu, Xinyi and Cao, Yue and Gao, Yi and Shen, Y. Ron and Liu, Wei-Tao},
abstractNote = {The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼−20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼−5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.},
doi = {10.1073/pnas.1802741115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 17,
volume = 115,
place = {United States},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1802741115

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