Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface

Beste, Ariana; Overbury, Steven H.

doi:10.1021/acs.jpcc.7b01431

Title: Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface

Abstract

We study methyl formate formation during methanol conversion on the fully oxidized and partially reduced ceria (111) surface using density functional theory. Starting from methanol and formaldehyde adsorbed on the surface, we consider two pathways of methyl formate production. Pathway 1 consists of formaldehyde dehydrogenation followed by oxygen–carbon bond formation. Along pathway 2, the oxygen–carbon bond is established prior to intermediate dehydrogenation. Formaldehyde production is observed at elevated temperature at which we expect both pathways to be energetically attainable on the fully oxidized surface. However, the probability of both reactants being adsorbed next to each other is low. This probability can be increased by the reduction of the surface. The partially reduced ceria surface is modeled by the introduction of an oxygen vacancy in the surface. If formaldehyde adsorbs over a vacancy, both pathways potentially contribute to methyl formate formation. In contrast, if methoxide that is obtained by dissociative adsorption of methanol is placed in the vacancy, methyl formate production becomes energetically highly demanding. Still, dehydrogenation of methoxide or methoxide exchange with coadsorbates converts methoxide in a vacancy to an active species for methyl formate formation while increasing the residence time of methoxide on the surface. Importantly, the preference ofmore »« less

Authors:

^[1];

^[2]

Univ. of Tennessee, Oak Ridge, TN (United States). Joint Inst. for Computational Sciences,
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Publication Date:: Tue May 02 00:00:00 EDT 2017

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

OSTI Identifier:: 1480467

Alternate Identifier(s):: OSTI ID: 1607320

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 18; 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


                    Beste, Ariana, and Overbury, Steven H. Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.jpcc.7b01431.

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                    Beste, Ariana, & Overbury, Steven H. Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface.  United States.  https://doi.org/10.1021/acs.jpcc.7b01431

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                    Beste, Ariana, and Overbury, Steven H. Tue .  
"Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface".  United States.  https://doi.org/10.1021/acs.jpcc.7b01431.  https://www.osti.gov/servlets/purl/1480467.

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@article{osti_1480467,

  title        = {Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface},

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

  abstractNote = {We study methyl formate formation during methanol conversion on the fully oxidized and partially reduced ceria (111) surface using density functional theory. Starting from methanol and formaldehyde adsorbed on the surface, we consider two pathways of methyl formate production. Pathway 1 consists of formaldehyde dehydrogenation followed by oxygen–carbon bond formation. Along pathway 2, the oxygen–carbon bond is established prior to intermediate dehydrogenation. Formaldehyde production is observed at elevated temperature at which we expect both pathways to be energetically attainable on the fully oxidized surface. However, the probability of both reactants being adsorbed next to each other is low. This probability can be increased by the reduction of the surface. The partially reduced ceria surface is modeled by the introduction of an oxygen vacancy in the surface. If formaldehyde adsorbs over a vacancy, both pathways potentially contribute to methyl formate formation. In contrast, if methoxide that is obtained by dissociative adsorption of methanol is placed in the vacancy, methyl formate production becomes energetically highly demanding. Still, dehydrogenation of methoxide or methoxide exchange with coadsorbates converts methoxide in a vacancy to an active species for methyl formate formation while increasing the residence time of methoxide on the surface. Importantly, the preference of pathway 1 is due to the promotion of surface-bound formaldehyde dehydrogenation by methoxide.},

  doi          = {10.1021/acs.jpcc.7b01431},

  journal      = {Journal of Physical Chemistry. C},

  number       = 18,

  volume       = 121,

  place        = {United States},

  year         = {Tue May 02 00:00:00 EDT 2017},

  month        = {Tue May 02 00:00:00 EDT 2017}

}

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Cited by: 4 works

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Figure 1: Reaction pathways to form methyl formate over ceria considered in this work.

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Title: Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface

Abstract

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

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Development of Low Temperature Three-Way Catalysts for Future Fuel Efficient Vehicles
journal, January 2015

Controlled synthesis and assembly of ceria-based nanomaterials
journal, July 2009

The role of ceria-based nanostructured materials in energy applications
journal, September 2014

Antioxidant Properties of Cerium Oxide Nanocrystals as a Function of Nanocrystal Diameter and Surface Coating
journal, October 2013

Biodistribution and biopersistence of ceria engineered nanomaterials: size dependence
journal, April 2013

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

Probing the Surface Sites of CeO ₂ Nanocrystals with Well-Defined Surface Planes via Methanol Adsorption and Desorption
journal, September 2012

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

The surface chemistry of cerium oxide
journal, March 2015

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

Adsorption and Reaction of Methanol over CeO _X (100) Thin Films
journal, March 2013

Methanol oxidation as a catalytic surface probe
journal, January 1997

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

Steam reforming of methanol over ceria and gold-ceria nanoshapes
journal, March 2010

Hydrogen Production from Methanol over Gold Supported on ZnO and CeO ₂ Nanoshapes
journal, September 2010

Methanol Selective Oxidation to Methyl Formate over ReOx/CeO2 Catalysts
journal, October 2007

Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment
journal, December 2012

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

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

Density Functional Theory Study of Methanol Decomposition on the CeO ₂ (110) Surface
journal, February 2008

Methanol adsorption on monocrystalline ceria surfaces
journal, April 2016

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

Performance of DFT+ U Approaches in the Study of Catalytic Materials
journal, November 2016

The influence of the Hubbard U parameter in simulating the catalytic behaviour of cerium oxide
journal, January 2014

A density functional theory study of formaldehyde adsorption and oxidation on CeO2(111) surface
journal, January 2010

Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
journal, September 2015

Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/Ceria
journal, October 2014

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

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

Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO ₂ (111)
journal, March 2016

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

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

Density-Functional Calculations of the Structure of Near-Surface Oxygen Vacancies and Electron Localization on ${CeO}_{2} (111)$
journal, January 2009

Evidence for Subsurface Ordering of Oxygen Vacancies on the Reduced ${CeO}_{2} (111)$ Surface Using Density-Functional and Statistical Calculations
journal, June 2013

Projector augmented-wave method
journal, December 1994

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

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

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

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

Generalized Gradient Approximation Made Simple
journal, October 1996

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

Hydrogen Cycle on CeO ₂ (111) Surfaces: Density Functional Theory Calculations
journal, October 2007

CO Adsorption and Oxidation on Ceria Surfaces from DFT+U Calculations
journal, May 2008

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

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

Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria
journal, December 2007

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

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

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Covalent radii revisited
journal, January 2008

Exploring the methanol decomposition mechanism on the Pt ₃ Ni(100) surface: a periodic density functional theory study
journal, January 2018