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Tetravalent doping of CeO2: the impact of valence electron character on group IV dopant influence

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Organization
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G.0802.09N
Project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
Fluorite CeO2 doped with group IV elements is studied within the density functional theory (DFT) and DFT + U framework. Concentration-dependent formation energies are calculated for Ce(1-x)Z(x)O(2) (Z = C, Si, Ge, Sn, Pb, Ti, Zr, Hf) with 0 <= x <= 0.25 and a roughly decreasing trend with ionic radius is observed. The influence of the valence and near valence electronic configuration is discussed, indicating the importance of filled d and f shells near the Fermi level for all properties investigated. A clearly different behavior of group IVa and IVb dopants is observed: the former are more suitable for surface modifications and the latter are more suitable for bulk modifications. For the entire set of group IV dopants, there exists an inverse relation between the change, due to doping, of the bulk modulus, and the thermal expansion coefficients. Hirshfeld-I atomic charges show that charge-transfer effects due to doping are limited to the nearest-neighbor oxygen atoms.
Keywords
bulk modulus, thermal expansion coefficients, materials science, simulation, atoms in molecules, CO OXIDATION, CRYSTAL-STRUCTURES, PERIODIC MATERIALS, NANOSIZED CEO2-SIO2, SOLID-SOLUTIONS, BUFFER LAYERS, SILICA-DOPED CERIA, AUGMENTED-WAVE METHOD, AIM, density functional theory, group IV, EXTENDING HIRSHFELD-I, CATALYSTS, DFT, ab-initio calculations, Ceria, VASP, doping, Cerium oxide

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Citation

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Chicago
Vanpoucke, Danny, Stefaan Cottenier, Veronique Van Speybroeck, Isabel Van Driessche, and Patrick Bultinck. 2014. “Tetravalent Doping of CeO2: The Impact of Valence Electron Character on Group IV Dopant Influence.” Journal of the American Ceramic Society 97 (1): 258–266.
APA
Vanpoucke, Danny, Cottenier, S., Van Speybroeck, V., Van Driessche, I., & Bultinck, P. (2014). Tetravalent doping of CeO2: the impact of valence electron character on group IV dopant influence. JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 97(1), 258–266.
Vancouver
1.
Vanpoucke D, Cottenier S, Van Speybroeck V, Van Driessche I, Bultinck P. Tetravalent doping of CeO2: the impact of valence electron character on group IV dopant influence. JOURNAL OF THE AMERICAN CERAMIC SOCIETY. 2014;97(1):258–66.
MLA
Vanpoucke, Danny, Stefaan Cottenier, Veronique Van Speybroeck, et al. “Tetravalent Doping of CeO2: The Impact of Valence Electron Character on Group IV Dopant Influence.” JOURNAL OF THE AMERICAN CERAMIC SOCIETY 97.1 (2014): 258–266. Print.
@article{4288632,
  abstract     = {Fluorite CeO2 doped with group IV elements is studied within the density functional theory (DFT) and DFT + U framework. Concentration-dependent formation energies are calculated for Ce(1-x)Z(x)O(2) (Z = C, Si, Ge, Sn, Pb, Ti, Zr, Hf) with 0 {\textlangle}= x {\textlangle}= 0.25 and a roughly decreasing trend with ionic radius is observed. The influence of the valence and near valence electronic configuration is discussed, indicating the importance of filled d and f shells near the Fermi level for all properties investigated. A clearly different behavior of group IVa and IVb dopants is observed: the former are more suitable for surface modifications and the latter are more suitable for bulk modifications. For the entire set of group IV dopants, there exists an inverse relation between the change, due to doping, of the bulk modulus, and the thermal expansion coefficients. Hirshfeld-I atomic charges show that charge-transfer effects due to doping are limited to the nearest-neighbor oxygen atoms.},
  author       = {Vanpoucke, Danny and Cottenier, Stefaan and Van Speybroeck, Veronique and Van Driessche, Isabel and Bultinck, Patrick},
  issn         = {0002-7820},
  journal      = {JOURNAL OF THE AMERICAN CERAMIC SOCIETY},
  keyword      = {bulk modulus,thermal expansion coefficients,materials science,simulation,atoms in molecules,CO OXIDATION,CRYSTAL-STRUCTURES,PERIODIC MATERIALS,NANOSIZED CEO2-SIO2,SOLID-SOLUTIONS,BUFFER LAYERS,SILICA-DOPED CERIA,AUGMENTED-WAVE METHOD,AIM,density functional theory,group IV,EXTENDING HIRSHFELD-I,CATALYSTS,DFT,ab-initio calculations,Ceria,VASP,doping,Cerium oxide},
  language     = {eng},
  number       = {1},
  pages        = {258--266},
  title        = {Tetravalent doping of CeO2: the impact of valence electron character on group IV dopant influence},
  url          = {http://dx.doi.org/10.1111/jace.12650},
  volume       = {97},
  year         = {2014},
}

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