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Title: Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

Abstract

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changes to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ringmore » and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.« less

Authors:
ORCiD logo;  [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [3]
  1. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Leipzig D-04103, Germany
  2. Department Chemie und Pharmazie, Friedrich-Alexander Universität Erlangen-Nürnberg, Erlangen D-91054, Germany
  3. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1457600
Report Number(s):
PNNL-SA-135743
Journal ID: ISSN 1932-7447; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Hensley, Alyssa J. R., Wöckel, Claudia, Gleichweit, Christoph, Gotterbarm, Karin, Papp, Christian, Steinrück, Hans-Peter, Wang, Yong, Denecke, Reinhard, and McEwen, Jean-Sabin. Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b10006.
Hensley, Alyssa J. R., Wöckel, Claudia, Gleichweit, Christoph, Gotterbarm, Karin, Papp, Christian, Steinrück, Hans-Peter, Wang, Yong, Denecke, Reinhard, & McEwen, Jean-Sabin. Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study. United States. doi:10.1021/acs.jpcc.7b10006.
Hensley, Alyssa J. R., Wöckel, Claudia, Gleichweit, Christoph, Gotterbarm, Karin, Papp, Christian, Steinrück, Hans-Peter, Wang, Yong, Denecke, Reinhard, and McEwen, Jean-Sabin. Fri . "Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study". United States. doi:10.1021/acs.jpcc.7b10006.
@article{osti_1457600,
title = {Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study},
author = {Hensley, Alyssa J. R. and Wöckel, Claudia and Gleichweit, Christoph and Gotterbarm, Karin and Papp, Christian and Steinrück, Hans-Peter and Wang, Yong and Denecke, Reinhard and McEwen, Jean-Sabin},
abstractNote = {Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changes to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.},
doi = {10.1021/acs.jpcc.7b10006},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 8,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}