Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111)

Sutton, Jonathan E.; Overbury, Steven H.; Beste, Ariana

doi:10.1021/acs.jpcc.6b02128

Title: Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO₂(111)

Abstract

Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO₂(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.

Authors:

Sutton, Jonathan E. ^[1]; Overbury, Steven H. ^[1]; Beste, Ariana ^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division

Publication Date:: Thu Mar 24 00:00:00 EDT 2016

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Org.:: DOE Office of Science (SC); USDOE

OSTI Identifier:: 1250415

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 120; Journal Issue: 13; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Sutton, Jonathan E., Overbury, Steven H., and Beste, Ariana. Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111).  United States: N. p., 2016. 
Web.  doi:10.1021/acs.jpcc.6b02128.

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                    Sutton, Jonathan E., Overbury, Steven H., & Beste, Ariana. Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111).  United States.  https://doi.org/10.1021/acs.jpcc.6b02128

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                    Sutton, Jonathan E., Overbury, Steven H., and Beste, Ariana. Thu .  
"Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111)".  United States.  https://doi.org/10.1021/acs.jpcc.6b02128.  https://www.osti.gov/servlets/purl/1250415.

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@article{osti_1250415,

  title        = {Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111)},

  author       = {Sutton, Jonathan E. and Overbury, Steven H. and Beste, Ariana},

  abstractNote = {Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.},

  doi          = {10.1021/acs.jpcc.6b02128},

  journal      = {Journal of Physical Chemistry. C},

  number       = 13,

  volume       = 120,

  place        = {United States},

  year         = {Thu Mar 24 00:00:00 EDT 2016},

  month        = {Thu Mar 24 00:00:00 EDT 2016}

}

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Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced ${CeO}_{2} (111)$
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Works referencing / citing this record:

Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production
journal, January 2020

Savara, Aditya
Reaction Kinetics, Mechanisms and Catalysis, Vol. 129, Issue 1
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Title: Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111)

Abstract

Citation Formats

Direct oxidation of hydrocarbons in a solid-oxide fuel cell journal, March 2000

Catalytic Properties of Ceria and CeO 2 -Containing Materials journal, November 1996

The surface chemistry of cerium oxide journal, March 2015

Methanol: A “Smart” Chemical Probe Molecule journal, September 2001

Adsorption and reaction of methanol on thin-film cerium oxide journal, April 2006

Adsorption and Reaction of C 1 −C 3 Alcohols over CeO X (111) Thin Films journal, July 2010

Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide journal, July 2013

Methanol Adsorption on the Clean CeO 2 (111) Surface: A Density Functional Theory Study journal, July 2007

Adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface: Dependence on the configuration of the cerium 4f electrons journal, January 2008

Reactions of Methanol with Pristine and Defective Ceria (111) Surfaces: A Comparison of Density Functionals journal, October 2014

Activity versus Selectivity of the Methanol Oxidation at Ceria Surfaces: A Comparative First-Principles Study journal, September 2015

Unraveling the structure sensitivity in methanol conversion on CeO2: A DFT+U study journal, July 2015

Hydrogen and methoxy coadsorption in the computation of the catalytic conversion of methanol on the ceria (111) surface journal, June 2016

Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO 2 ( 111 ) journal, October 2015

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

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A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal, April 2010

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal, December 2000

A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal, December 2000

Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production journal, January 2020

Title: Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO₂(111)

Direct oxidation of hydrocarbons in a solid-oxide fuel cell
journal, March 2000

Catalytic Properties of Ceria and CeO ₂ -Containing Materials
journal, November 1996

The surface chemistry of cerium oxide
journal, March 2015

Methanol: A “Smart” Chemical Probe Molecule
journal, September 2001

Adsorption and reaction of methanol on thin-film cerium oxide
journal, April 2006

Adsorption and Reaction of C ₁ −C ₃ Alcohols over CeO _X (111) Thin Films
journal, July 2010

Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide
journal, July 2013

Methanol Adsorption on the Clean CeO ₂ (111) Surface: A Density Functional Theory Study
journal, July 2007

Adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface: Dependence on the configuration of the cerium 4f electrons
journal, January 2008

Reactions of Methanol with Pristine and Defective Ceria (111) Surfaces: A Comparison of Density Functionals
journal, October 2014

Activity versus Selectivity of the Methanol Oxidation at Ceria Surfaces: A Comparative First-Principles Study
journal, September 2015

Unraveling the structure sensitivity in methanol conversion on CeO2: A DFT+U study
journal, July 2015

Hydrogen and methoxy coadsorption in the computation of the catalytic conversion of methanol on the ceria (111) surface
journal, June 2016

Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced ${CeO}_{2} (111)$
journal, October 2015

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Projector augmented-wave method
journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Generalized Gradient Approximation Made Simple
journal, October 1996

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production
journal, January 2020