Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping
Abstract
Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F––Ce4+ resonant enhancement feature suggests that this bond is at least partially covalent. Here, our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.
- Authors:
-
- Charles Univ., Prague (Czech Republic); Friedrich-Alexander-Univ. Erlangen-Nürnberg, Erlangen (Germany)
- Charles Univ., Prague (Czech Republic); Forschungszentrum Jülich, Julich (Germany)
- Uppsala Univ., Uppsala (Sweden); Univ. of Bath, Bath (United Kingdom)
- Uppsala Univ., Uppsala (Sweden)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Charles Univ., Prague (Czech Republic)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1557709
- Report Number(s):
- BNL-211941-2019-JAAM
Journal ID: ISSN 0021-9606
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 151; Journal Issue: 4; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Citation Formats
Kettner, Miroslav, Duchoň, Tomáš, Wolf, Matthew J., Kullgren, Jolla, Senanayake, Sanjaya D., Hermansson, Kersti, Veltruská, Kateřina, and Nehasil, Václav. Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping. United States: N. p., 2019.
Web. doi:10.1063/1.5109955.
Kettner, Miroslav, Duchoň, Tomáš, Wolf, Matthew J., Kullgren, Jolla, Senanayake, Sanjaya D., Hermansson, Kersti, Veltruská, Kateřina, & Nehasil, Václav. Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping. United States. https://doi.org/10.1063/1.5109955
Kettner, Miroslav, Duchoň, Tomáš, Wolf, Matthew J., Kullgren, Jolla, Senanayake, Sanjaya D., Hermansson, Kersti, Veltruská, Kateřina, and Nehasil, Václav. Mon .
"Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping". United States. https://doi.org/10.1063/1.5109955. https://www.osti.gov/servlets/purl/1557709.
@article{osti_1557709,
title = {Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping},
author = {Kettner, Miroslav and Duchoň, Tomáš and Wolf, Matthew J. and Kullgren, Jolla and Senanayake, Sanjaya D. and Hermansson, Kersti and Veltruská, Kateřina and Nehasil, Václav},
abstractNote = {Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F––Ce4+ resonant enhancement feature suggests that this bond is at least partially covalent. Here, our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.},
doi = {10.1063/1.5109955},
journal = {Journal of Chemical Physics},
number = 4,
volume = 151,
place = {United States},
year = {Mon Jul 22 00:00:00 EDT 2019},
month = {Mon Jul 22 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Optimization of ionic conductivity in doped ceria
journal, February 2006
- Andersson, D. A.; Simak, S. I.; Skorodumova, N. V.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 10
Structure and Reducibility of CeO 2 Doped with Trivalent Cations
journal, October 2016
- Lucid, Aoife K.; Keating, Patrick R. L.; Allen, Jeremy P.
- The Journal of Physical Chemistry C, Vol. 120, Issue 41
A combination of directing groups and chiral anion phase-transfer catalysis for enantioselective fluorination of alkenes
journal, August 2013
- Wu, Jeffrey; Wang, Yi-Ming; Drljevic, Amela
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 34
The progression of chiral anions from concepts to applications in asymmetric catalysis
journal, July 2012
- Phipps, Robert J.; Hamilton, Gregory L.; Toste, F. Dean
- Nature Chemistry, Vol. 4, Issue 8
Fundamentals and Catalytic Applications of CeO 2 -Based Materials
journal, April 2016
- Montini, Tiziano; Melchionna, Michele; Monai, Matteo
- Chemical Reviews, Vol. 116, Issue 10
The surface chemistry of cerium oxide
journal, March 2015
- Mullins, David R.
- Surface Science Reports, Vol. 70, Issue 1
Growth, Structure, and Stability of Ceria Films on Si(111) and the Application of CaF 2 Buffer Layers
journal, June 2005
- Zarraga-Colina, Jeannette; Nix, Roger M.; Weiss, Helmut
- The Journal of Physical Chemistry B, Vol. 109, Issue 21
Performance, structure, and mechanism of CeO2 in HCl oxidation to Cl2
journal, February 2012
- Amrute, Amol P.; Mondelli, Cecilia; Moser, Maximilian
- Journal of Catalysis, Vol. 286
Morphology and nanostructure of CeO2(111) surfaces of single crystals and Si(111) supported ceria films
journal, January 2012
- Pieper, H. H.; Derks, C.; Zoellner, M. H.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 44
Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides
journal, July 2001
- Asahi, R.
- Science, Vol. 293, Issue 5528
Anion (Fluoride)-Doped Ceria Nanocrystals: Synthesis, Characterization, and Its Catalytic Application to Oxidative Coupling of Benzylamines
journal, December 2013
- Ahmad, Shahzad; Gopalaiah, Kovuru; Chandrudu, Sankala Naga
- Inorganic Chemistry, Vol. 53, Issue 4
Promotional effect of fluorine on the selective catalytic reduction of NO with NH3 over CeO2-TiO2 catalyst at low temperature
journal, January 2014
- Zhang, Rui; Zhong, Qin; Zhao, Wei
- Applied Surface Science, Vol. 289
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions
journal, January 2015
- Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik
- Nature Communications, Vol. 6, Issue 1
Cerium Oxyfluoride and Its Lattice Structure
journal, September 1950
- Finkelnburg, Wolfgang; Stein, Adam
- The Journal of Chemical Physics, Vol. 18, Issue 9
Preparation and Properties of tho Rare Earth Fluorides and Oxyfluorides
journal, August 1954
- Popov, Alexander I.; Knudson, George E.
- Journal of the American Chemical Society, Vol. 76, Issue 15
Unit Cell Dimensions of Some Rare Earth Oxyfluorides
journal, September 1954
- Baenziger, N. C.; Holden, J. R.; Knudson, G. E.
- Journal of the American Chemical Society, Vol. 76, Issue 18
Reaction between rare earth oxides and elemental fluorine. II. Kinetics of the fluorination of cerium dioxide
journal, April 1992
- Takashima, Masayuki; Fukami, Shinji; Nosaka, Yoshihiro
- Journal of Fluorine Chemistry, Vol. 57, Issue 1-3
Pt–CeO x thin film catalysts for PEMFC
journal, February 2015
- Fiala, R.; Vaclavu, M.; Rednyk, A.
- Catalysis Today, Vol. 240
Influence of the Ce–F interaction on cerium photoelectron spectra in CeO F layers
journal, October 2015
- Kettner, M.; Ševčíková, K.; Homola, P.
- Chemical Physics Letters, Vol. 639
Fluorine impurities at CeO 2 (111): Effects on oxygen vacancy formation, molecular adsorption, and surface re-oxidation
journal, January 2017
- Wolf, Matthew J.; Kullgren, Jolla; Broqvist, Peter
- The Journal of Chemical Physics, Vol. 146, Issue 4
Relationships between complex core level spectra and materials properties
journal, August 2010
- Nelin, C. J.; Bagus, P. S.; Ilton, E. S.
- International Journal of Quantum Chemistry, Vol. 110, Issue 15
Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state
journal, January 2016
- Bagus, Paul S.; Nelin, Connie J.; Al-Salik, Yahya
- Surface Science, Vol. 643
Covalent bonding in heavy metal oxides
journal, April 2017
- Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.
- The Journal of Chemical Physics, Vol. 146, Issue 13
Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment
journal, December 2012
- Paier, Joachim; Penschke, Christopher; Sauer, Joachim
- Chemical Reviews, Vol. 113, Issue 6
Morphology and CO Oxidation Reactions on Anion Doped CeO X F Y /Rh(111) and CeO X /Rh(111) Inverse Catalysts
journal, September 2016
- Kettner, M.; Ševčíková, K.; Duchoň, T.
- The Journal of Physical Chemistry C, Vol. 120, Issue 47
Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain
journal, May 2017
- Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul
- Nature Communications, Vol. 8, Issue 1
Water Dissociation on CeO 2 (100) and CeO 2 (111) Thin Films
journal, August 2012
- Mullins, David R.; Albrecht, Peter M.; Chen, Tsung-Liang
- The Journal of Physical Chemistry C, Vol. 116, Issue 36
High-resolution photoemission study of ethanol on Si(100)2×1
journal, February 2000
- Casaletto, M. P.; Zanoni, R.; Carbone, M.
- Surface Science, Vol. 447, Issue 1-3
Methanol adsorption on a CeO2(111)/Cu(111) thin film model catalyst
journal, April 2009
- Matolín, V.; Libra, J.; Škoda, M.
- Surface Science, Vol. 603, Issue 8
Atomically Dispersed Pd, Ni, and Pt Species in Ceria-Based Catalysts: Principal Differences in Stability and Reactivity
journal, April 2016
- Neitzel, Armin; Figueroba, Alberto; Lykhach, Yaroslava
- The Journal of Physical Chemistry C, Vol. 120, Issue 18
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014
- Graciani, J.; Mudiyanselage, K.; Xu, F.
- Science, Vol. 345, Issue 6196
Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces
journal, January 2016
- Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G.
- Nature Physics, Vol. 12, Issue 5
Covalent versus localized nature of electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory
journal, April 2017
- Duchoň, Tomáš; Aulická, Marie; Schwier, Eike F.
- Physical Review B, Vol. 95, Issue 16
Calculations of electron inelastic mean free paths. X. Data for 41 elemental solids over the 50 eV to 200 keV range with the relativistic full Penn algorithm: Calculations of electron inelastic mean free paths. X
journal, July 2015
- Shinotsuka, H.; Tanuma, S.; Powell, C. J.
- Surface and Interface Analysis, Vol. 47, Issue 9
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 124, Issue 21
Hybrid functionals applied to rare-earth oxides: The example of ceria
journal, January 2007
- Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim
- Physical Review B, Vol. 75, Issue 4
Screened hybrid functionals applied to ceria: Effect of Fock exchange
journal, June 2018
- Du, Dou; Wolf, Matthew J.; Hermansson, Kersti
- Physical Review B, Vol. 97, Issue 23
Ordered Phases of Reduced Ceria As Epitaxial Films on Cu(111)
journal, December 2013
- Duchoň, Tomáš; Dvořák, Filip; Aulická, Marie
- The Journal of Physical Chemistry C, Vol. 118, Issue 1
Covalent interactions in oxides
journal, June 2014
- Bagus, Paul S.; Nelin, Connie J.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy
journal, January 2014
- Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin
- The Journal of Physical Chemistry C, Vol. 118, Issue 4
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
The nature of the electronic band gap in lanthanide oxides
text, January 2012
- Gillen, Roland; Clark, Stewart J.; Robertson, John
- arXiv