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Title: The surface chemistry of cerium oxide

Abstract

Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

Authors:
 [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1185722
Alternate Identifier(s):
OSTI ID: 1365421
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Surface Science Reports
Additional Journal Information:
Journal Volume: 70; Journal Issue: 1; Journal ID: ISSN 0167-5729
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ceria; thin films; scanning tunneling microscopy; temperature programmed desorption; photoelectron spectroscopy; chemisorption

Citation Formats

Mullins, David R. The surface chemistry of cerium oxide. United States: N. p., 2015. Web. doi:10.1016/j.surfrep.2014.12.001.
Mullins, David R. The surface chemistry of cerium oxide. United States. https://doi.org/10.1016/j.surfrep.2014.12.001
Mullins, David R. Thu . "The surface chemistry of cerium oxide". United States. https://doi.org/10.1016/j.surfrep.2014.12.001. https://www.osti.gov/servlets/purl/1185722.
@article{osti_1185722,
title = {The surface chemistry of cerium oxide},
author = {Mullins, David R.},
abstractNote = {Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.},
doi = {10.1016/j.surfrep.2014.12.001},
journal = {Surface Science Reports},
number = 1,
volume = 70,
place = {United States},
year = {Thu Jan 29 00:00:00 EST 2015},
month = {Thu Jan 29 00:00:00 EST 2015}
}

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Healing of oxygen vacancies on reduced surfaces of gold-doped ceria
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Evidence for Weakly Bound Oxygen on Ceria Films
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Water Chemistry on Model Ceria and Pt/Ceria Catalysts
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Interaction of D 2 O with CeO 2 (001) Investigated by Temperature-Programmed Desorption and X-ray Photoelectron Spectroscopy
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Probing the reaction intermediates for the water–gas shift over inverse CeOx/Au(111) catalysts
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Water adsorption on the stoichiometric and reduced CeO2(111) surface: a first-principles investigation
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First-Principles Assessment of H 2 S and H 2 O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO 2 (111) Surface
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Water Adsorption and Its Effect on the Stability of Low Index Stoichiometric and Reduced Surfaces of Ceria
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Insight into the Adsorption of Water on the Clean CeO 2 (111) Surface with van der Waals and Hybrid Density Functionals
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Interaction of CO with Rh Supported on Stoichiometric and Reduced CeO2(111) andCeO2(100) Surfaces
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Metal–support interactions between Pt and thin film cerium oxide
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The reaction of carbon monoxide with palladium supported on cerium oxide thin films
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An ab initio study of CO adsorption on ceria(110)
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CO adsorption on CeO2(110) using hybrid-DFT embedded-cluster calculations
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Ab initio calculations of CO physisorption on ceria(111)
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Strong and weak adsorption of CO on CeO2 surfaces from first principles calculations
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A DFT+U study of the lattice oxygen reactivity toward direct CO oxidation on the CeO2(111) and (110) surfaces
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The Surface Dependence of CO Adsorption on Ceria
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CO2 activation on single crystal based ceria and magnesia/ceria model catalysts
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Ceria reoxidation by CO2: A model study
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Coverage Effect of the CO 2 Adsorption Mechanisms on CeO 2 (111) by First Principles Analysis
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Reaction of NO on CeO2 and Rh/CeO2 thin films supported on α-Al2O3(0001) and YSZ(100)
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Evidence of a lacunar mechanism for deNOx activity in ceria-based catalysts
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Adsorption of NO on unreduced and reduced CeO2 surfaces: A plane-wave DFT study
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Chemistry of NO2 on CeO2 and MgO: Experimental and theoretical studies on the formation of NO3
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Reduction of NO 2 on Ceria Surfaces
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Electron correlation contribution to the /ceria(111) interaction
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Chemisorption and Reaction of Sulfur Dioxide with Oxidized and Reduced Ceria Surfaces
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Study of ceria sulfation
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Interaction of Al 2 O 3 and CeO 2 Surfaces with SO 2 and SO 2 + O 2 Studied by X-ray Photoelectron Spectroscopy
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TPD and XPS Investigation of the Interaction of SO2 with Model Ceria Catalysts
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Mechanism of Sulfur Poisoning and Storage: Adsorption and Reaction of SO 2 with Stoichiometric and Reduced Ceria Films on Cu(111)
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Sulfidation and Sulfur Recovery from SO 2 over Ceria
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A First-Principles Analysis for Sulfur Tolerance of CeO 2 in Solid Oxide Fuel Cells
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Adsorption and reaction of hydrogen sulfide on thin-film cerium oxide
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Interaction between NO and C 2 H 4 on Rh-Loaded CeO X (111)
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The reaction of ethylene on a model automotive emissions control catalyst
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Ceria in Hydrogenation Catalysis: High Selectivity in the Conversion of Alkynes to Olefins
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Molecular-Level Understanding of CeO 2 as a Catalyst for Partial Alkyne Hydrogenation
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Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide
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Methanol: A “Smart” Chemical Probe Molecule
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Adsorption and reaction of methanol on thin-film cerium oxide
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Methanol Adsorption on the Clean CeO 2 (111) Surface:  A Density Functional Theory Study
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Density Functional Theory Study of Methanol Decomposition on the CeO 2 (110) Surface
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Adsorption and Reaction of Methanol over CeO X (100) Thin Films
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Methanol oxidation as a catalytic surface probe
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Adsorption and Reaction of C 1 −C 3 Alcohols over CeO X (111) Thin Films
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Isopropanol oxidation by pure metal oxide catalysts: number of active surface sites and turnover frequencies
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Ethylene Glycol Adsorption and Reaction over CeO X (111) Thin Films
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Adsorption and Reaction of Acetaldehyde over CeO X (111) Thin Films
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Dehydration of diols catalyzed by CeO2
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Theoretical investigation of 1,3-butanediol adsorption on an oxygen-defected CeO2(111) surface
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PIO study on 1,3-butanediol dehydration over CeO2 (111) surface
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Adsorption and reaction of formaldehyde on thin-film cerium oxide
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Adsorption and Reaction of Acetone over CeO x (111) Thin Films
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Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts
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Acetone Chemistry on Oxidized and Reduced TiO 2 (110)
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A density functional theory study of formaldehyde adsorption on ceria
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Inner-shell spectroscopy of p-benzoquinone, hydroquinone, and phenol: distinguishing quinoid and benzenoid structures
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Adsorption and reaction of methanethiol on thin-film cerium oxide
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Dimethyl methylphosphonate decomposition on fully oxidized and partially reduced ceria thin films
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Gold supported on well-ordered ceria films: nucleation, growth and morphology in CO oxidation reaction
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Effect of Ceria Support on the Structure of Ni Nanoparticles
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Nature of Ag Islands and Nanoparticles on the CeO 2 (111) Surface
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Ag Adsorption on Reduced CeO 2 (111) Thin Films
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Interaction of Gold with Cerium Oxide Supports: CeO 2 (111) Thin Films vs CeO x Nanoparticles
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Gold Adsorption on CeO 2 Thin Films Grown on Ru(0001)
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Interactions of Ni Nanoparticles with Reducible CeO 2 (111) Thin Films
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Growth of Pt Nanoparticles on Reducible CeO 2 (111) Thin Films: Effect of Nanostructures and Redox Properties of Ceria
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Redox Behavior of the Model Catalyst Pd/CeO 2− x /Pt(111)
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Formation of alumina–ceria mixed oxide in model systems
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A photoemission study of the interaction of Ga with CeO2(111) thin films
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Ti/CeOx(111) interfaces studied by XPS and STM
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Interaction of tungsten with CeO 2 (111) layers as a function of temperature: a photoelectron spectroscopy study
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Density Functional Theory Study of the Interaction of Cu, Ag, and Au Atoms with the Regular CeO 2 (111) Surface
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First-principles investigation of transition metal atom M (M = Cu, Ag, Au) adsorption on CeO2(110)
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Electronic states of metal (Cu, Ag, Au) atom on CeO2(111) surface: The role of local structural distortion
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Au on (111) and (110) surfaces of CeO2: A density-functional theory study
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A DFT Study of the Structures of Aux Clusters on a CeO2(111) Surface
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Anchoring Sites for Initial Au Nucleation on CeO 2 {111}: O Vacancy versus Ce Vacancy
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Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation
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Positive Charge States and Possible Polymorphism of Gold Nanoclusters on Reduced Ceria
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The Adsorption Properties of Cu and Ni on the Ceria(111) Surface
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Thermodynamic, electronic and structural properties of Cu/CeO2 surfaces and interfaces from first-principles DFT+U calculations
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Origin of the High Activity of the Ceria-Supported Copper Catalyst for H 2 O Dissociation
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Oxygen vacancy formation energy at the Pd/CeO2(111) interface
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On the adsorption and formation of Pt dimers on the CeO 2 (111) surface
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Adsorption, Oxidation State, and Diffusion of Pt Atoms on the CeO 2 (111) Surface
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Formation of a Rhodium Surface Oxide Film in Rh n /CeO 2 (111) Relevant for Catalytic CO Oxidation: A Computational Study
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Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding
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Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts
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Palladium interaction with CeO 2 , Sn–Ce–O and Ga–Ce–O layers
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CO Adsorption on the Model Catalyst Pd/CeO 2- x (111)/Rh(111)
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CO Oxidation at the Interface of Au Nanoclusters and the Stepped-CeO 2 (111) Surface by the Mars–van Krevelen Mechanism
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