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Title: Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110)

Abstract

The competitive interaction between acetone and two solvent molecules (methanol and water) for surface sites on rutile TiO2(110) was studied using temperature programmed desorption (TPD). On a vacuum reduced TiO2(110) surface, which possessed ~5% oxygen vacancy sites, excess methanol displaced preadsorbed acetone molecules to weakly bound and physisorbed desorption states below 200 K, whereas acetone was stabilized to 250 K against displacement by methanol on an oxidized surface through formation of an acetone-diolate species. These behaviors of acetone differ from the competitive interactions between acetone and water in that acetone is less susceptible to displacement by water. Examination of acetone+methanol and acetone+water multilayer combinations shows that acetone is more compatible in water-ice films than in methanol-ice films, presumably because water has greater potential as a hydrogen-bond donor than does methanol. Acetone molecules displaced from the TiO2(110) surface by water are more likely to be retained in the near-surface region, having a greater opportunity to revisit the surface, than when methanol is used as a coadsorbate. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1025082
Report Number(s):
PNNL-SA-79870
Journal ID: ISSN 0743-7463; LANGD5; 35219; KC0302010; TRN: US201120%%266
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Langmuir, 27(15):9430-9438
Additional Journal Information:
Journal Volume: 27; Journal Issue: 15; Journal ID: ISSN 0743-7463
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; ACETONE; DESORPTION; METHANOL; OXYGEN; RUTILE; SOLVENTS; WATER; TiO2; photocatalysis; acetone; methanol; water; Environmental Molecular Sciences Laboratory

Citation Formats

Shen, Mingmin, and Henderson, Michael A. Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110). United States: N. p., 2011. Web. doi:10.1021/la2016726.
Shen, Mingmin, & Henderson, Michael A. Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110). United States. https://doi.org/10.1021/la2016726
Shen, Mingmin, and Henderson, Michael A. 2011. "Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110)". United States. https://doi.org/10.1021/la2016726.
@article{osti_1025082,
title = {Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110)},
author = {Shen, Mingmin and Henderson, Michael A},
abstractNote = {The competitive interaction between acetone and two solvent molecules (methanol and water) for surface sites on rutile TiO2(110) was studied using temperature programmed desorption (TPD). On a vacuum reduced TiO2(110) surface, which possessed ~5% oxygen vacancy sites, excess methanol displaced preadsorbed acetone molecules to weakly bound and physisorbed desorption states below 200 K, whereas acetone was stabilized to 250 K against displacement by methanol on an oxidized surface through formation of an acetone-diolate species. These behaviors of acetone differ from the competitive interactions between acetone and water in that acetone is less susceptible to displacement by water. Examination of acetone+methanol and acetone+water multilayer combinations shows that acetone is more compatible in water-ice films than in methanol-ice films, presumably because water has greater potential as a hydrogen-bond donor than does methanol. Acetone molecules displaced from the TiO2(110) surface by water are more likely to be retained in the near-surface region, having a greater opportunity to revisit the surface, than when methanol is used as a coadsorbate. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.},
doi = {10.1021/la2016726},
url = {https://www.osti.gov/biblio/1025082}, journal = {Langmuir, 27(15):9430-9438},
issn = {0743-7463},
number = 15,
volume = 27,
place = {United States},
year = {Tue Aug 02 00:00:00 EDT 2011},
month = {Tue Aug 02 00:00:00 EDT 2011}
}