Adsorption and Reactions of ClCH2CH2OH on Clean and Oxygen-Precovered Cu(100): Experimental and Computational Studies

Temperature-programmed reaction/desorption, reflection−absorption infrared spectroscopy, and density functional theory calculations have been employed to investigate the adsorption and thermal reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100) surfaces. On Cu(100), ClCH2CH2OH is mainly a...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2005-10, Vol.109 (40), p.18921-18928
Main Authors: Fu, Tao-Wei, Liao, Yung-Hsuan, Chen, Chia-Yuan, Chang, Pei-Teng, Wang, Ching-Yung, Lin, Jong-Liang
Format: Article
Language:English
Subjects:
Adsorption
Computer Simulation
Copper - chemistry
Ethylene Chlorohydrin - chemistry
Models, Chemical
Oxygen - chemistry
Sensitivity and Specificity
Spectroscopy, Fourier Transform Infrared - methods
Surface Properties
Temperature
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Summary:Temperature-programmed reaction/desorption, reflection−absorption infrared spectroscopy, and density functional theory calculations have been employed to investigate the adsorption and thermal reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100) surfaces. On Cu(100), ClCH2CH2OH is mainly adsorbed reversibly. The ClCH2CH2OH molecules at a submonolayer coverage can change their orientation with increasing temperature. However, on oxygen-precovered Cu(100), all of the adsorbed ClCH2CH2OH molecules below 0.5 langmuir exposures completely dissociate to generate ethylene and acetaldehyde via the intermediate of ClCH2CH2O−. The computational studies predict that the ClCH2CH2O− is most likely to be adsorbed at the 4-fold hollow sites of Cu(100), with its C−O bond only slightly titled away from the surface normal and with a gauche conformation with respect to the C−C bond. The hollow-site ClCH2CH2O− has an adsorption energy that is 4.4 and 19.2 kcal·mol-1 lower than that of the ClCH2CH2O− bonded at the bridging and atop sites, respectively. No significant effect of precovered oxygen on the ClCH2CH2O− bonding geometry and infrared band frequencies has been observed, as compared with the case without oxygen.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp052309g