globalchange  > 气候变化与战略
DOI: 10.1073/pnas.1802741115
论文题名:
Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy
作者: Yang D.; Li Y.; Liu X.; Cao Y.; Gao Y.; Shen Y.R.; Liu W.-T.
刊名: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
出版年: 2018
卷: 115, 期:17
起始页码: E3888
结束页码: E3894
语种: 英语
英文关键词: Adsorption configuration ; Facet effect ; Fermi resonance ; Sum-frequency ; Titanium dioxide ; Vibration spectroscopy
Scopus关键词: methanol ; methanol derivative ; methyl group ; oxygen ; titanium dioxide ; ab initio calculation ; adsorption kinetics ; analytic method ; Article ; dissociation ; energy transfer ; environmental temperature ; extraction ; hydrogen bond ; isotherm ; molecular interaction ; pressure ; priority journal ; sensitivity analysis ; sum frequency vibrational spectroscopy ; surface property
英文摘要: The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO2), 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 TiO2, 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. © 2018 National Academy of Sciences. All Rights Reserved.
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资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/163723
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作者单位: Yang, D., State Key Laboratory of Surface Physics, Physics Department, Fudan University, Shanghai, 200433, China, Key Laboratory of Micro and Nano Photonic Structures, Fudan University, Shanghai, 200433, China; Li, Y., Division of Interfacial Water, Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China; Liu, X., State Key Laboratory of Surface Physics, Physics Department, Fudan University, Shanghai, 200433, China, Key Laboratory of Micro and Nano Photonic Structures, Fudan University, Shanghai, 200433, China; Cao, Y., State Key Laboratory of Surface Physics, Physics Department, Fudan University, Shanghai, 200433, China, Key Laboratory of Micro and Nano Photonic Structures, Fudan University, Shanghai, 200433, China; Gao, Y., Division of Interfacial Water, Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China; Shen, Y.R., State Key Laboratory of Surface Physics, Physics Department, Fudan University, Shanghai, 200433, China, Key Laboratory of Micro and Nano Photonic Structures, Fudan University, Shanghai, 200433, China, Department of Physics, University of California, Berkeley, CA 94720, United States; Liu, W.-T., State Key Laboratory of Surface Physics, Physics Department, Fudan University, Shanghai, 200433, China, Key Laboratory of Micro and Nano Photonic Structures, Fudan University, Shanghai, 200433, China, Collaborative Innovation Center of Advanced Microstructures, Nanjing, 210093, China

Recommended Citation:
Yang D.,Li Y.,Liu X.,et al. Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy[J]. Proceedings of the National Academy of Sciences of the United States of America,2018-01-01,115(17)
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