Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping

Kettner, Miroslav; Duchoň, Tomáš; Wolf, Matthew J.; Kullgren, Jolla; Senanayake, Sanjaya D.; Hermansson, Kersti; Veltruská, Kateřina; Nehasil, Václav

doi:10.1063/1.5109955

Title: Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping

Journal Article · 22 July 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5109955 · OSTI ID:1557709

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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)

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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1557709

Report Number(s):: BNL-211941-2019-JAAM

Journal Information:: Journal of Chemical Physics, Vol. 151, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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References (47)

Optimization of ionic conductivity in doped ceria Andersson, D. A.; Simak, S. I.; Skorodumova, N. V. Proceedings of the National Academy of Sciences, Vol. 103, Issue 10 https://doi.org/10.1073/pnas.0509537103	journal	February 2006
Electronic perturbations Campbell, Charles T. Nature Chemistry, Vol. 4, Issue 8 https://doi.org/10.1038/nchem.1412	journal	July 2012
Structure and Reducibility of CeO ₂ Doped with Trivalent Cations Lucid, Aoife K.; Keating, Patrick R. L.; Allen, Jeremy P. The Journal of Physical Chemistry C, Vol. 120, Issue 41 https://doi.org/10.1021/acs.jpcc.6b08118	journal	October 2016
A combination of directing groups and chiral anion phase-transfer catalysis for enantioselective fluorination of alkenes Wu, Jeffrey; Wang, Yi-Ming; Drljevic, Amela Proceedings of the National Academy of Sciences, Vol. 110, Issue 34 https://doi.org/10.1073/pnas.1304346110	journal	August 2013
The progression of chiral anions from concepts to applications in asymmetric catalysis Phipps, Robert J.; Hamilton, Gregory L.; Toste, F. Dean Nature Chemistry, Vol. 4, Issue 8 https://doi.org/10.1038/nchem.1405	journal	July 2012
Fundamentals and Catalytic Applications of CeO ₂ -Based Materials Montini, Tiziano; Melchionna, Michele; Monai, Matteo Chemical Reviews, Vol. 116, Issue 10 https://doi.org/10.1021/acs.chemrev.5b00603	journal	April 2016
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
Growth, Structure, and Stability of Ceria Films on Si(111) and the Application of CaF ₂ Buffer Layers Zarraga-Colina, Jeannette; Nix, Roger M.; Weiss, Helmut The Journal of Physical Chemistry B, Vol. 109, Issue 21 https://doi.org/10.1021/jp0508296	journal	June 2005
Performance, structure, and mechanism of CeO2 in HCl oxidation to Cl2 Amrute, Amol P.; Mondelli, Cecilia; Moser, Maximilian Journal of Catalysis, Vol. 286 https://doi.org/10.1016/j.jcat.2011.11.016	journal	February 2012
Morphology and nanostructure of CeO2(111) surfaces of single crystals and Si(111) supported ceria films Pieper, H. H.; Derks, C.; Zoellner, M. H. Physical Chemistry Chemical Physics, Vol. 14, Issue 44 https://doi.org/10.1039/c2cp42733h	journal	January 2012
Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides Asahi, R. Science, Vol. 293, Issue 5528 https://doi.org/10.1126/science.1061051	journal	July 2001
Anion (Fluoride)-Doped Ceria Nanocrystals: Synthesis, Characterization, and Its Catalytic Application to Oxidative Coupling of Benzylamines Ahmad, Shahzad; Gopalaiah, Kovuru; Chandrudu, Sankala Naga Inorganic Chemistry, Vol. 53, Issue 4 https://doi.org/10.1021/ic403166q	journal	December 2013
Promotional effect of fluorine on the selective catalytic reduction of NO with NH3 over CeO2-TiO2 catalyst at low temperature Zhang, Rui; Zhong, Qin; Zhao, Wei Applied Surface Science, Vol. 289 https://doi.org/10.1016/j.apsusc.2013.10.143	journal	January 2014
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7097	journal	January 2015
Cerium Oxyfluoride and Its Lattice Structure Finkelnburg, Wolfgang; Stein, Adam The Journal of Chemical Physics, Vol. 18, Issue 9 https://doi.org/10.1063/1.1747929	journal	September 1950
Preparation and Properties of tho Rare Earth Fluorides and Oxyfluorides Popov, Alexander I.; Knudson, George E. Journal of the American Chemical Society, Vol. 76, Issue 15 https://doi.org/10.1021/ja01644a016	journal	August 1954
Unit Cell Dimensions of Some Rare Earth Oxyfluorides Baenziger, N. C.; Holden, J. R.; Knudson, G. E. Journal of the American Chemical Society, Vol. 76, Issue 18 https://doi.org/10.1021/ja01647a073	journal	September 1954
Reaction between rare earth oxides and elemental fluorine. II. Kinetics of the fluorination of cerium dioxide Takashima, Masayuki; Fukami, Shinji; Nosaka, Yoshihiro Journal of Fluorine Chemistry, Vol. 57, Issue 1-3 https://doi.org/10.1016/s0022-1139(00)82824-9	journal	April 1992
Pt–CeO x thin film catalysts for PEMFC Fiala, R.; Vaclavu, M.; Rednyk, A. Catalysis Today, Vol. 240 https://doi.org/10.1016/j.cattod.2014.03.069	journal	February 2015
Influence of the Ce–F interaction on cerium photoelectron spectra in CeO F layers Kettner, M.; Ševčíková, K.; Homola, P. Chemical Physics Letters, Vol. 639 https://doi.org/10.1016/j.cplett.2015.09.018	journal	October 2015
Fluorine impurities at CeO ₂ (111): Effects on oxygen vacancy formation, molecular adsorption, and surface re-oxidation Wolf, Matthew J.; Kullgren, Jolla; Broqvist, Peter The Journal of Chemical Physics, Vol. 146, Issue 4 https://doi.org/10.1063/1.4973239	journal	January 2017
Relationships between complex core level spectra and materials properties Nelin, C. J.; Bagus, P. S.; Ilton, E. S. International Journal of Quantum Chemistry, Vol. 110, Issue 15 https://doi.org/10.1002/qua.22807	journal	August 2010
Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state Bagus, Paul S.; Nelin, Connie J.; Al-Salik, Yahya Surface Science, Vol. 643 https://doi.org/10.1016/j.susc.2015.06.002	journal	January 2016
Covalent bonding in heavy metal oxides Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4979018	journal	April 2017
Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment Paier, Joachim; Penschke, Christopher; Sauer, Joachim Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr3004949	journal	December 2012
Morphology and CO Oxidation Reactions on Anion Doped CeO _X F _Y /Rh(111) and CeO _X /Rh(111) Inverse Catalysts Kettner, M.; Ševčíková, K.; Duchoň, T. The Journal of Physical Chemistry C, Vol. 120, Issue 47 https://doi.org/10.1021/acs.jpcc.6b07431	journal	September 2016
Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15360	journal	May 2017
Water Dissociation on CeO ₂ (100) and CeO ₂ (111) Thin Films Mullins, David R.; Albrecht, Peter M.; Chen, Tsung-Liang The Journal of Physical Chemistry C, Vol. 116, Issue 36 https://doi.org/10.1021/jp306444h	journal	August 2012
High-resolution photoemission study of ethanol on Si(100)2×1 Casaletto, M. P.; Zanoni, R.; Carbone, M. Surface Science, Vol. 447, Issue 1-3 https://doi.org/10.1016/s0039-6028(99)01197-8	journal	February 2000
Methanol adsorption on a CeO2(111)/Cu(111) thin film model catalyst Matolín, V.; Libra, J.; Škoda, M. Surface Science, Vol. 603, Issue 8 https://doi.org/10.1016/j.susc.2009.02.010	journal	April 2009
Atomically Dispersed Pd, Ni, and Pt Species in Ceria-Based Catalysts: Principal Differences in Stability and Reactivity Neitzel, Armin; Figueroba, Alberto; Lykhach, Yaroslava The Journal of Physical Chemistry C, Vol. 120, Issue 18 https://doi.org/10.1021/acs.jpcc.6b02264	journal	April 2016
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014
Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G. Nature Physics, Vol. 12, Issue 5 https://doi.org/10.1038/nphys3627	journal	January 2016
Covalent versus localized nature of 4 f electrons in ceria: Resonant angle-resolved photoemission spectroscopy and density functional theory Duchoň, Tomáš; Aulická, Marie; Schwier, Eike F. Physical Review B, Vol. 95, Issue 16 https://doi.org/10.1103/physrevb.95.165124	journal	April 2017
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 Shinotsuka, H.; Tanuma, S.; Powell, C. J. Surface and Interface Analysis, Vol. 47, Issue 9 https://doi.org/10.1002/sia.5789	journal	July 2015
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.2204597	journal	June 2006
Hybrid functionals applied to rare-earth oxides: The example of ceria Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim Physical Review B, Vol. 75, Issue 4 https://doi.org/10.1103/physrevb.75.045121	journal	January 2007
Screened hybrid functionals applied to ceria: Effect of Fock exchange Du, Dou; Wolf, Matthew J.; Hermansson, Kersti Physical Review B, Vol. 97, Issue 23 https://doi.org/10.1103/physrevb.97.235203	journal	June 2018
Ordered Phases of Reduced Ceria As Epitaxial Films on Cu(111) Duchoň, Tomáš; Dvořák, Filip; Aulická, Marie The Journal of Physical Chemistry C, Vol. 118, Issue 1 https://doi.org/10.1021/jp409220p	journal	December 2013
Covalent interactions in oxides Bagus, Paul S.; Nelin, Connie J. Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2013.11.004	journal	June 2014
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin The Journal of Physical Chemistry C, Vol. 118, Issue 4 https://doi.org/10.1021/jp410644j	journal	January 2014
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
The nature of the electronic band gap in lanthanide oxides Gillen, Roland; Clark, Stewart J.; Robertson, John arXiv https://doi.org/10.48550/arxiv.1208.0503	text	January 2012