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Title: Ultrafast dynamics of acetone photooxidation on TiO2(110)

Abstract

Using light energy to drive chemical reactions on semiconductor surfaces is the basis for technological applications ranging from the removal of organic pollutants to the generation of renewable solar fuels, yet our understanding of the mechanisms has been hindered by the multistep nature of the process and the wide range of time scales over which it occurs (femtoseconds to seconds). In this work, we use ultrafast laser pump-probe techniques to follow the time evolution of substrate-induced photooxidation of acetone on a titania surface. A UV light at 260 nm initiates carrier-induced fragmentation of adsorbed acetone on a TiO2(110) surface that was pretreated with oxygen. The photoreaction results in the ejection of methyl radicals into the gas-phase that are detected by the probe pulse via resonant multiphoton ionization. The time evolution of the methyl radicals leaving the surface exhibits ultrafast rise times, 300–700 fs, followed by a more gradual rise that plateaus by 10 ps, with faster rates at a low acetone coverage. Furthermore, these results are interpreted in terms of a time-dependent rate expression and a mechanism in which the fragmentation of the acetone surface species is driven by interactions with nonequilibrium, “hot” holes.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Stony Brook Univ., Stony Brook, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1572365
Alternate Identifier(s):
OSTI ID: 1572584
Report Number(s):
BNL-212234-2019-JAAM
Journal ID: ISSN 0021-9606; TRN: US2001236
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Muraca, Amanda R., Kershis, Matthew D., Camillone, III, Nicholas, and White, Michael G. Ultrafast dynamics of acetone photooxidation on TiO2(110). United States: N. p., 2019. Web. doi:10.1063/1.5122269.
Muraca, Amanda R., Kershis, Matthew D., Camillone, III, Nicholas, & White, Michael G. Ultrafast dynamics of acetone photooxidation on TiO2(110). United States. doi:10.1063/1.5122269.
Muraca, Amanda R., Kershis, Matthew D., Camillone, III, Nicholas, and White, Michael G. Thu . "Ultrafast dynamics of acetone photooxidation on TiO2(110)". United States. doi:10.1063/1.5122269. https://www.osti.gov/servlets/purl/1572365.
@article{osti_1572365,
title = {Ultrafast dynamics of acetone photooxidation on TiO2(110)},
author = {Muraca, Amanda R. and Kershis, Matthew D. and Camillone, III, Nicholas and White, Michael G.},
abstractNote = {Using light energy to drive chemical reactions on semiconductor surfaces is the basis for technological applications ranging from the removal of organic pollutants to the generation of renewable solar fuels, yet our understanding of the mechanisms has been hindered by the multistep nature of the process and the wide range of time scales over which it occurs (femtoseconds to seconds). In this work, we use ultrafast laser pump-probe techniques to follow the time evolution of substrate-induced photooxidation of acetone on a titania surface. A UV light at 260 nm initiates carrier-induced fragmentation of adsorbed acetone on a TiO2(110) surface that was pretreated with oxygen. The photoreaction results in the ejection of methyl radicals into the gas-phase that are detected by the probe pulse via resonant multiphoton ionization. The time evolution of the methyl radicals leaving the surface exhibits ultrafast rise times, 300–700 fs, followed by a more gradual rise that plateaus by 10 ps, with faster rates at a low acetone coverage. Furthermore, these results are interpreted in terms of a time-dependent rate expression and a mechanism in which the fragmentation of the acetone surface species is driven by interactions with nonequilibrium, “hot” holes.},
doi = {10.1063/1.5122269},
journal = {Journal of Chemical Physics},
number = 16,
volume = 151,
place = {United States},
year = {2019},
month = {10}
}

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