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Title: Surface Structure Dependence of the Dry Dehydrogenation of Alcohols on Cu(111) and Cu(110)

Authors:
 [1]; ;  [1];  [1]; ; ORCiD logo; ORCiD logo [1]
  1. Department of Chemistry, Tufts University, Medford, Massachusetts 02155, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388884
DOE Contract Number:
SC0012573
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 121; Journal Issue: 23; Related Information: IMASC partners with Harvard University (lead); Fritz Haber Institute; Lawrence Berkeley National Laboratory; Lawrence Livermore National Laboratory; University of Kansas; Tufts University
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), mesostructured materials, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Wang, Zhi-Tao, Xu, Yunfei, El-Soda, Mostafa, Lucci, Felicia R., Madix, Robert J., Friend, Cynthia M., and Sykes, E. Charles H.. Surface Structure Dependence of the Dry Dehydrogenation of Alcohols on Cu(111) and Cu(110). United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02957.
Wang, Zhi-Tao, Xu, Yunfei, El-Soda, Mostafa, Lucci, Felicia R., Madix, Robert J., Friend, Cynthia M., & Sykes, E. Charles H.. Surface Structure Dependence of the Dry Dehydrogenation of Alcohols on Cu(111) and Cu(110). United States. doi:10.1021/acs.jpcc.7b02957.
Wang, Zhi-Tao, Xu, Yunfei, El-Soda, Mostafa, Lucci, Felicia R., Madix, Robert J., Friend, Cynthia M., and Sykes, E. Charles H.. Mon . "Surface Structure Dependence of the Dry Dehydrogenation of Alcohols on Cu(111) and Cu(110)". United States. doi:10.1021/acs.jpcc.7b02957.
@article{osti_1388884,
title = {Surface Structure Dependence of the Dry Dehydrogenation of Alcohols on Cu(111) and Cu(110)},
author = {Wang, Zhi-Tao and Xu, Yunfei and El-Soda, Mostafa and Lucci, Felicia R. and Madix, Robert J. and Friend, Cynthia M. and Sykes, E. Charles H.},
abstractNote = {},
doi = {10.1021/acs.jpcc.7b02957},
journal = {Journal of Physical Chemistry. C},
number = 23,
volume = 121,
place = {United States},
year = {Mon Jun 05 00:00:00 EDT 2017},
month = {Mon Jun 05 00:00:00 EDT 2017}
}
  • The adsorption and reaction of ethanol, propan-1-ol, and propan-2-ol have been studied on clean and oxygen-covered copper(110) by using a thermal molecular beam. The preadsorption of oxygen greatly enhances the sticking probability of all the alcohols, although a saturated coverage (p (2 {times} 1) LEED pattern) poisons the oxidative dehydrogenation reaction. The reaction mechanism has been worked out in detail with the help of isotopic labeling experiments and is common to all alcohols examined. There is a change of stoichiometry observed with temperature, at low temperatures (at ambient or just above) 2R{sub 1}R{sub 2}CHOH + O{sub (a)} {yields} 2R{sub 1}R{submore » 2}CO + H{sub 2}O + H{sub 2}, changing to R{sub 1}R{sub 2}CHOH + O{sub (a)} {yields} R{sub 1}R{sub 2}CO + H{sub 2}O at higher temperature, the exact temperature depending on the alcohol involved. The rate of reaction follows the stability of the intermediate alkoxy species except for 2-propoxy which shows a slower rate than expected. This effect and the poisoning observed for saturation coverages of preadsorbed oxygen are due to the stabilization of the alkoxy species by coadsorbed surface hydroxyl groups or oxygen atoms. Overall the reaction rate is limited by the decomposition of the alkoxy species.« less
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  • A study of the growth of Fe on Cu{l brace}111{r brace} and on Cu{l brace}110{r brace} has been carried out with low-energy electron diffraction (LEED) and Auger electron spectroscopy. We find that on Cu{l brace}111{r brace}, Fe grows first pseudomorphically as {gamma}-Fe{l brace}111{r brace} to a thickness of about five layer equivalents (LE), and then forms six bcc Fe{l brace}110{r brace} domains rotationally related in the Kurdjumov-Sachs orientation. The pseudomorphic film has the same bulk interlayer spacing, within experimental error, as the Cu{l brace}111{r brace} substrate (2.08{plus minus}0.03 A) and a slightly contracted first interlayer spacing (2.03{plus minus}0.03 A). Withmore » increasing thickness more and more defects are introduced in the film, but a 13-LE film still produces a good LEED pattern. On Cu{l brace}110{r brace}, the Fe film grows also pseudomorphically, with the same bulk interlayer spacing as the substrate (1.27 A) and a contracted first interlayer spacing (1.17 A), but a precise structure analysis is not possible because the film has relatively large {l brace}111{r brace} facets. Defects and disorder increase with film thickness, so that the LEED pattern is practically obliterated when the thickness exceeds about 20 LE.« less
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