skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1];  [2]
  1. 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)
  2. 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:
Journal Article: 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. 2016. "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},
url = {https://www.osti.gov/biblio/1248781}, journal = {Physical Chemistry Chemical Physics. PCCP},
issn = {1463-9076},
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


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


A density functional theory study of formaldehyde adsorption on ceria
journal, November 2007


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


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


The Entropies of Adsorbed Molecules
journal, October 2012


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


Many competing ceria (110) oxygen vacancy structures: From small to large supercells
journal, July 2012


Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces
journal, January 2015


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


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


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


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


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


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


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


Nudged elastic band method for finding minimum energy paths of transitions
conference, November 2011

  • JÓNsson, Hannes; Mills, Greg; Jacobsen, Karsten W.
  • Proceedings of the International School of Physics, Classical and Quantum Dynamics in Condensed Phase Simulations
  • https://doi.org/10.1142/9789812839664_0016

The surface chemistry of cerium oxide
journal, March 2015


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


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


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


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


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


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


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


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


The electronic structure of oxygen vacancy defects at the low index surfaces of ceria
journal, December 2005


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


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


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


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


Isopropanol oxidation by pure metal oxide catalysts: number of active surface sites and turnover frequencies
journal, November 2002


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


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


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


Surface properties of CeO 2 from first principles
journal, February 2004


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


Thermal desorption of gases
journal, July 1962


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


Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020


High-resolution X-ray luminescence extension imaging
journal, February 2021


Works referencing / citing this record: