Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions

Journal Article · · Journal of Materials Chemistry. A
DOI: https://doi.org/10.1039/C9TA11784A · OSTI ID:1603285
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [4];  [5];  [2];  [2];  [2];  [6];  [6]; ORCiD logo [7];  [8]
  1. Peter-Grünberg-Inst. (Germany); Charles Univ., Prague (Czech Republic)
  2. Peter-Grünberg-Inst. (Germany)
  3. Uppsala Univ. (Sweden)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Lab. Nacional de Luz Síncrotron (Brazil)
  6. Charles Univ., Prague (Czech Republic)
  7. Peter-Grünberg-Inst. (Germany); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Peter-Grünberg-Inst. (Germany) ; Univ. of California, Davis, CA (United States)
+ Show Author Affiliations

The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure–reducibility relationship under identical conditions. Kinetic rate constants of Ce4+ to Ce3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; AC02-05CH11231
OSTI ID:
1603285
Alternate ID(s):
OSTI ID: 1598714; OSTI ID: 1775374
Report Number(s):
BNL-213669-2020-JAAM; JMCAET
Journal Information:
Journal of Materials Chemistry. A, Vol. 8, Issue 11; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (51)

Structure–Activity Map of Ceria Nanoparticles, Nanocubes, and Mesoporous Architectures journal August 2016
Highly Enhanced Concentration and Stability of Reactive Ce 3+ on Doped CeO 2 Surface Revealed In Operando journal May 2012
Polarity driven morphology of CeO2(100) islands on Cu(111) journal November 2013
Projector augmented-wave method journal December 1994
Hybrid functionals based on a screened Coulomb potential journal May 2003
Catalysis by Doped Oxides journal December 2012
Spillover Reoxidation of Ceria Nanoparticles journal May 2016
Three-Dimensional Valency Mapping in Ceria Nanocrystals journal October 2014
Unusual Redox Behavior of Ceria and Its Interaction with Hydrogen journal August 2019
Reduction kinetics of ceria surface by hydrogen journal July 2004
Evidence of Subsurface Oxygen Vacancy Ordering on Reduced CeO 2 ( 111 ) journal August 2007
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces journal June 2016
Fast vacancy-mediated oxygen ion incorporation across the ceria–gas electrochemical interface journal July 2014
Structure sensitivity of catalytic reactions journal February 1986
Effect of Ceria Structure on Oxygen Migration for Rh/Ceria Catalysts journal January 1996
Electronic structure of nanoporous ceria from x-ray absorption spectroscopy and atomic multiplet calculations journal December 2007
Facet-dependent electrochemical properties of Co3O4 nanocrystals toward heavy metal ions journal October 2013
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal June 2006
CeO 2 ↔ CuO x Interactions and the Controlled Assembly of CeO 2 (111) and CeO 2 (100) Nanoparticles on an Oxidized Cu(111) Substrate journal October 2011
Growth and characterization of epitaxially stabilized ceria(001) nanostructures on Ru(0001) journal January 2016
Ab initiomolecular dynamics for liquid metals journal January 1993
Facet-Dependent and Light-Assisted Efficient Hydrogen Evolution from Ammonia Borane Using Gold-Palladium Core-Shell Nanocatalysts journal May 2016
Model Studies in Heterogeneous Catalysis journal July 2010
The surface science of titanium dioxide journal January 2003
Water Adsorption and Its Effect on the Stability of Low Index Stoichiometric and Reduced Surfaces of Ceria journal March 2012
The Synergy between Metal Facet and Oxide Support Facet for Enhanced Catalytic Performance: The Case of Pd–TiO 2 journal July 2016
Controlling Heteroepitaxy by Oxygen Chemical Potential: Exclusive Growth of (100) Oriented Ceria Nanostructures on Cu(111) journal January 2016
Single-Molecule Nanocatalysis Reveals Facet-Dependent Catalytic Kinetics and Dynamics of Pallidium Nanoparticles journal March 2017
Unraveling the Dynamic Nanoscale Reducibility (Ce 4+ → Ce 3+ ) of CeO x -Ru in Hydrogen Activation journal September 2015
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Entropic contributions enhance polarity compensation for CeO2(100) surfaces journal November 2016
Evidence for Subsurface Ordering of Oxygen Vacancies on the Reduced CeO 2 ( 111 ) Surface Using Density-Functional and Statistical Calculations journal June 2013
Oxidation of Reduced Ceria by Incorporation of Hydrogen journal September 2019
The surface chemistry of cerium oxide journal March 2015
Oxygen-Vacancy Dynamics and Entanglement with Polaron Hopping at the Reduced CeO 2 ( 111 ) Surface journal March 2019
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal May 1994
The cubic-to-hexagonal phase transition of cerium oxide particles: dynamics and structure journal January 2017
Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment journal December 2012
In situ growth, structure, and real-time chemical reactivity of well-defined CeOx-Ru(0001) model surfaces journal November 2016
Faceted metal and metal oxide nanoparticles: design, fabrication and catalysis journal January 2015
Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite journal July 2016
Determination of Ce4+/Ce3+ in electron-beam-damaged CeO2 by electron energy-loss spectroscopy journal December 1999
Opposite Face Sensitivity of CeO 2 in Hydrogenation and Oxidation Catalysis journal August 2014
Ceria Nanocrystals Exposing Wide (100) Facets: Structure and Polarity Compensation journal November 2014
Calculation of electron inelastic mean free paths (IMFPs) VII. Reliability of the TPP-2M IMFP predictive equation journal January 2003
The probing depth of total electron yield in the sub-keV range: TEY-XAS and X-PEEM journal July 2003
On the growth mechanisms of polar (100) surfaces of ceria on copper (100) journal May 2018
Fundamentals and Catalytic Applications of CeO 2 -Based Materials journal April 2016
X-ray absorption studies of CeO 2 , PrO 2 , and TbO 2 . I. Manifestation of localized and extended f states in the 3 d absorption spectra journal July 1987
Redox Kinetics Study of Fuel Reduced Ceria for Chemical-Looping Water Splitting journal July 2016
Surface controlled reduction kinetics of nominally undoped polycrystalline CeO 2 journal January 2015

Similar Records

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY