Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces
Abstract
We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.
- Authors:
-
- Joint Institute for Computational Sciences, The Univ. of Tennessee, Oak Ridge (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1248781
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 15; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Beste, Ariana, and Overbury, Steven H. Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces. United States: N. p., 2016.
Web. doi:10.1039/C6CP00151C.
Beste, Ariana, & Overbury, Steven H. Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces. United States. https://doi.org/10.1039/C6CP00151C
Beste, Ariana, and Overbury, Steven H. Wed .
"Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces". United States. https://doi.org/10.1039/C6CP00151C. https://www.osti.gov/servlets/purl/1248781.
@article{osti_1248781,
title = {Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces},
author = {Beste, Ariana and Overbury, Steven H.},
abstractNote = {We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.},
doi = {10.1039/C6CP00151C},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 15,
volume = 18,
place = {United States},
year = {Wed Mar 09 00:00:00 EST 2016},
month = {Wed Mar 09 00:00:00 EST 2016}
}
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Works referencing / citing this record:
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