Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)

Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; Xu, Ye

doi:10.1016/j.cattod.2015.03.033

Title: Reactivity and reaction intermediates for acetic acid adsorbed on CeO₂(111)

Abstract

Adsorption and reaction of acetic acid on a CeO₂(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO₂ surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone and acetic acid desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.

Authors:

Calaza, Florencia C. ^[1]; Chen, Tsung -Liang ^[1]; Mullins, David R. ^[1]; Xu, Ye ^[2]; Steven H. Overbury

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Louisiana State Univ., Baton Rouge, LA (United States)

Publication Date:: Sat May 02 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

OSTI Identifier:: 1185988

Alternate Identifier(s):: OSTI ID: 1251819

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Catalysis Today

Additional Journal Information:: Journal Volume: 253; Journal ID: ISSN 0920-5861

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CeO2(111); acetic acid; ketonization; vacancies; TPD; sXPS; NEXAFS; DFT; oxide catalysis; surface chemistry; acetic acid adsorption

Citation Formats


                    Calaza, Florencia C., Chen, Tsung -Liang, Mullins, David R., Xu, Ye, and Steven H. Overbury. Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111).  United States: N. p., 2015. 
Web.  doi:10.1016/j.cattod.2015.03.033.

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                    Calaza, Florencia C., Chen, Tsung -Liang, Mullins, David R., Xu, Ye, & Steven H. Overbury. Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111).  United States.  https://doi.org/10.1016/j.cattod.2015.03.033

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                    Calaza, Florencia C., Chen, Tsung -Liang, Mullins, David R., Xu, Ye, and Steven H. Overbury. Sat .  
"Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)".  United States.  https://doi.org/10.1016/j.cattod.2015.03.033.  https://www.osti.gov/servlets/purl/1185988.

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@article{osti_1185988,

  title        = {Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)},

  author       = {Calaza, Florencia C. and Chen, Tsung -Liang and Mullins, David R. and Xu, Ye and Steven H. Overbury},

  abstractNote = {Adsorption and reaction of acetic acid on a CeO2(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO2 surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone and acetic acid desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.},

  doi          = {10.1016/j.cattod.2015.03.033},

  journal      = {Catalysis Today},

  number       = ,

  volume       = 253,

  place        = {United States},

  year         = {Sat May 02 00:00:00 EDT 2015},

  month        = {Sat May 02 00:00:00 EDT 2015}

}

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Title: Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)

Abstract

Citation Formats

Ceria-Based Solid Catalysts for Organic Chemistry journal, May 2010

The surface chemistry of cerium oxide journal, March 2015

Surface structure dependence of selective oxidation of ethanol on faceted CeO2 nanocrystals journal, October 2013

Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO 2 Nanocrystals: Elucidation of Structure–Function Relationships journal, June 2014

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Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion journal, October 2013

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Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal, September 1992

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Ab initiomolecular dynamics for liquid metals journal, January 1993

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Comment on “Taming multiple valency with density functionals: A case study of defective ceria” journal, December 2005

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

First-principles LDA + U and GGA + U study of cerium oxides: Dependence on the effective U parameter journal, January 2007

Modeling of Ce O 2 , Ce 2 O 3 , and Ce O 2 − x in the LDA + U formalism journal, January 2007

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

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) journal, December 1992

Special points for Brillouin-zone integrations journal, June 1976

An object-oriented scripting interface to a legacy electronic structure code journal, January 2002

Infrared intensities and Raman-scattering activities within density-functional theory journal, September 1996

Adsorption and reaction of H2O and CO on oxidized and reduced Rh/CeOx(111) surfaces journal, June 2000

Adsorption and Reaction of Acetone over CeO x (111) Thin Films journal, March 2009

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

Fluorination effects on the inner-shell spectra of unsaturated molecules journal, January 1988

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

Adsorption and Reaction of Acetaldehyde over CeO X (111) Thin Films journal, February 2011

Density Functional Theory Study of Carboxylic Acids Adsorption and Enolization on Monoclinic Zirconia Surfaces journal, July 2011

Acetaldehyde Adsorption and Reaction on CeO 2 (100) Thin Films journal, July 2013

Ethylene Glycol Adsorption and Reaction over CeO X (111) Thin Films journal, June 2011

Inner-shell spectroscopy of p-benzoquinone, hydroquinone, and phenol: distinguishing quinoid and benzenoid structures journal, August 1992

Unfilled orbitals of C60 and C70 from carbon K-shell X-ray absorption fine structure journal, August 1991

Structural studies of argon-sputtered amorphous carbon films by means of extended x-ray-absorption fine structure journal, October 1988

NEXAFS investigations of transition metal oxides, nitrides, carbides, sulfides and other interstitial compounds journal, January 1997

Electronic Structure of Cubic Refractory Carbides journal, April 1971

Ideal gas thermodynamic properties of methanoic and ethanoic acids journal, January 1978

Pathways for carboxylic acid decomposition on titania journal, July 1988

Reaction of carboxylic acids on CeO2(111) and CeO2(100) journal, September 1996

Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination journal, October 1980

On the intermediates of the acetic acid reactions on oxides: an IR study journal, October 1996

Selective Adsorption to Particular Crystal Faces of ZnO journal, April 2012

Modeling the antisymmetric and symmetric stretching vibrational modes of aqueous carboxylate anions journal, January 2015

Oxide-catalyzed conversion of acetic acid into acetone: an FTIR spectroscopic investigation journal, March 2003

The formation of ketones and aldehydes from carboxylic acids, structure-activity relationship for two competitive reactions journal, November 1995

Reactions of Carboxylic Acids on Oxides journal, June 1997

Redox Pathways for HCOOH Decomposition over CeO 2 Surfaces journal, June 2008

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal, October 2011

Reaction between methanol and acetic acid catalyzed by SiO 2 ‐supported V‐P‐O catalyst in oxygen atmosphere journal, July 2019

Catalytic Pyrolysis of Aliphatic Carboxylic Acids into Symmetric Ketones over Ceria-Based Catalysts: Kinetics, Isotope Effect and Mechanism journal, February 2020

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons journal, March 2017

CO 2 electrochemical reduction at thiolate-modified bulk Au electrodes journal, January 2019

Surface chemistry of rare-earth oxide surfaces at ambient conditions: Reactions with water and hydrocarbons text, January 2017

Catalytic deoxygenation of model compounds from flash pyrolysis of lignocellulosic biomass over activated charcoal-based catalysts journal, December 2017

An Experimental Study of the Acetic Acid Steam Reforming Over Co-Based Catalysts journal, December 2020

Title: Reactivity and reaction intermediates for acetic acid adsorbed on CeO₂(111)

Ceria-Based Solid Catalysts for Organic Chemistry
journal, May 2010

The surface chemistry of cerium oxide
journal, March 2015

Surface structure dependence of selective oxidation of ethanol on faceted CeO2 nanocrystals
journal, October 2013

Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO ₂ Nanocrystals: Elucidation of Structure–Function Relationships
journal, June 2014

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

Oxygen Vacancy-Assisted Coupling and Enolization of Acetaldehyde on CeO ₂ (111)
journal, October 2012

Condensation reactions of propanal over CexZr1−xO2 mixed oxide catalysts
journal, September 2010

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications
journal, February 2013

Distinguishing Enolic and Carbonyl Components in the Mechanism of Carboxylic Acid Ketonization on Monoclinic Zirconia
journal, July 2012

Ketonization of Carboxylic Acids in Biomass Conversion over TiO ₂ and ZrO ₂ Surfaces: A DFT Perspective
journal, July 2014

Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion
journal, October 2013

Reassignment of the Vibrational Spectra of Carbonates, Formates, and Related Surface Species on Ceria: A Combined Density Functional and Infrared Spectroscopy Investigation
journal, November 2011

Temperature evolution of structure and bonding of formic acid and formate on fully oxidized and highly reduced CeO2(111)
journal, January 2009

Ordered cerium oxide thin films grown on Ru(0001) and Ni(111)
journal, June 1999

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

Reactions of methanol on W(100) and W(100)-(5 $times; 1)C surfaces
journal, April 1980

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Comment on “Taming multiple valency with density functionals: A case study of defective ceria”
journal, December 2005

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

First-principles $LDA + U$ and $GGA + U$ study of cerium oxides: Dependence on the effective U parameter
journal, January 2007

Modeling of $Ce O_{2}$ , ${Ce}_{2} O_{3}$ , and $Ce O_{2 - x}$ in the $LDA + U$ formalism
journal, January 2007

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

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992

Special points for Brillouin-zone integrations
journal, June 1976

An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

Infrared intensities and Raman-scattering activities within density-functional theory
journal, September 1996

Adsorption and reaction of H2O and CO on oxidized and reduced Rh/CeOx(111) surfaces
journal, June 2000

Adsorption and Reaction of Acetone over CeO _x (111) Thin Films
journal, March 2009

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

Fluorination effects on the inner-shell spectra of unsaturated molecules
journal, January 1988

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

Adsorption and Reaction of Acetaldehyde over CeO _X (111) Thin Films
journal, February 2011

Density Functional Theory Study of Carboxylic Acids Adsorption and Enolization on Monoclinic Zirconia Surfaces
journal, July 2011

Acetaldehyde Adsorption and Reaction on CeO ₂ (100) Thin Films
journal, July 2013

Ethylene Glycol Adsorption and Reaction over CeO _X (111) Thin Films
journal, June 2011

Inner-shell spectroscopy of p-benzoquinone, hydroquinone, and phenol: distinguishing quinoid and benzenoid structures
journal, August 1992

Unfilled orbitals of C60 and C70 from carbon K-shell X-ray absorption fine structure
journal, August 1991

Structural studies of argon-sputtered amorphous carbon films by means of extended x-ray-absorption fine structure
journal, October 1988

NEXAFS investigations of transition metal oxides, nitrides, carbides, sulfides and other interstitial compounds
journal, January 1997

Electronic Structure of Cubic Refractory Carbides
journal, April 1971

Ideal gas thermodynamic properties of methanoic and ethanoic acids
journal, January 1978

Pathways for carboxylic acid decomposition on titania
journal, July 1988

Reaction of carboxylic acids on CeO2(111) and CeO2(100)
journal, September 1996

Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination
journal, October 1980

On the intermediates of the acetic acid reactions on oxides: an IR study
journal, October 1996

Selective Adsorption to Particular Crystal Faces of ZnO
journal, April 2012

Modeling the antisymmetric and symmetric stretching vibrational modes of aqueous carboxylate anions
journal, January 2015

Oxide-catalyzed conversion of acetic acid into acetone: an FTIR spectroscopic investigation
journal, March 2003

The formation of ketones and aldehydes from carboxylic acids, structure-activity relationship for two competitive reactions
journal, November 1995

Reactions of Carboxylic Acids on Oxides
journal, June 1997

Redox Pathways for HCOOH Decomposition over CeO ₂ Surfaces
journal, June 2008

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Reaction between methanol and acetic acid catalyzed by SiO 2 ‐supported V‐P‐O catalyst in oxygen atmosphere
journal, July 2019

Catalytic Pyrolysis of Aliphatic Carboxylic Acids into Symmetric Ketones over Ceria-Based Catalysts: Kinetics, Isotope Effect and Mechanism
journal, February 2020

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons
journal, March 2017

CO ₂ electrochemical reduction at thiolate-modified bulk Au electrodes
journal, January 2019

Surface chemistry of rare-earth oxide surfaces at ambient conditions: Reactions with water and hydrocarbons
text, January 2017

Catalytic deoxygenation of model compounds from flash pyrolysis of lignocellulosic biomass over activated charcoal-based catalysts
journal, December 2017

An Experimental Study of the Acetic Acid Steam Reforming Over Co-Based Catalysts
journal, December 2020