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Title: Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

Abstract

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.

Authors:
ORCiD logo [1];  [2];  [3];  [4]
  1. Department of Chemistry and Chemical Biology; Harvard University; Cambridge; USA
  2. Department of Chemistry and Chemical Biology; Harvard University; Cambridge; USA; School of Engineering and Applied Sciences
  3. Parks College of Engineering, Aviation and Technology; Saint Louis University; Saint Louis; USA; The Langmuir Research Institute
  4. School of Engineering and Applied Sciences; Harvard University; Cambridge; USA
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:
1387300
DOE Contract Number:  
SC0012573
Resource Type:
Journal Article
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 188; Related Information: IMASC partners with Harvard University (lead); Fritz Haber Institute; Lawrence Berkeley National Laboratory; Lawrence Livermore National Laboratory; University of Kansas; Tufts University; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), mesostructured materials, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Wang, Lu-Cun, Friend, C. M., Fushimi, Rebecca, and Madix, Robert J. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts. United States: N. p., 2016. Web. doi:10.1039/C5FD00161G.
Wang, Lu-Cun, Friend, C. M., Fushimi, Rebecca, & Madix, Robert J. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts. United States. doi:10.1039/C5FD00161G.
Wang, Lu-Cun, Friend, C. M., Fushimi, Rebecca, and Madix, Robert J. Fri . "Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts". United States. doi:10.1039/C5FD00161G.
@article{osti_1387300,
title = {Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts},
author = {Wang, Lu-Cun and Friend, C. M. and Fushimi, Rebecca and Madix, Robert J.},
abstractNote = {The activation of molecular O2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.},
doi = {10.1039/C5FD00161G},
journal = {Faraday Discussions},
issn = {1359-6640},
number = ,
volume = 188,
place = {United States},
year = {2016},
month = {1}
}

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