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Inorganics
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Rare Earth-Doped Ceria Systems and Their Applications
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Rare Earth-Doped Ceria Systems and Their Applications

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Inorganic Solid-State Chemistry".

Deadline for manuscript submissions: closed (29 February 2020) | Viewed by 13548

Special Issue Editor

Dr. Cristina Artini

E-Mail Website
Guest Editor
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova, Via Dodecaneso 31, 16146 Genova, Italy
Interests: solid state chemistry; powder X-ray diffraction; Raman spectroscopy; ionic conductivity; thermoelectricity; materials for energy; functional oxides; rare earth oxides; intermetallics

Special Issue Information

Dear Colleagues,

The remarkable values of ionic conductivity shown by ceria, when doped with proper amounts of trivalent lanthanide ions, have been well known since the seventies of the last century. Nevertheless, it has only been in the last few years that interest has increased in the production of sustainable energy, coupled with the relatively easy access to synchrotron facilities, which has allowed for the investigation of subtle crystallographic details. This has made doped ceria an attractive and widely studied material for use as an electrolyte in solid oxide fuel and electrolysis cells, working in the intermediate temperature range (400–700 °C). These issues justify the large number of experimental and theoretical studies focusing on doped ceria that have appeared in the literature in the last decade.

Ionic conductivity in doped ceria occurs thanks to oxygen diffusion, through vacancies introduced by substituting tetravalent Ce from the trivalent rare earth. The partial Ce substitution involves important structural modifications both on an average and local scale, such as lattice distortion, dopant segregation and clustering, precipitation of nanosized defects, and so on. All of these aspects directly reflect on the physical properties, and even more so on the temperature and compositional range of employment of the material.

This Special Issue is intended to collect contributions regarding crystallography, physical features, and the use of doped ceria in solid oxide cells, with the main aim of highlighting the correlation between the structure, properties, and applications of this material.

Dr. Cristina Artini
Guest Editor

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Keywords

  • rare earth-doped ceria
  • ionic conductivity
  • solid oxide fuel cells
  • solid oxide electrolysis cells
  • structure–properties correlation
  • average structure
  • local structure

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Published Papers (4 papers)

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Research

11 pages, 2164 KiB  
Article
Influence of Nanoscale Surface Arrangements on the Oxygen Transfer Ability of Ceria–Zirconia Mixed Oxide
by Eleonora Aneggi, Carla de Leitenburg and Alessandro Trovarelli
Inorganics 2020, 8(5), 34; https://doi.org/10.3390/inorganics8050034 - 12 May 2020
Cited by 5 | Viewed by 2678
Abstract
Ceria-based materials, and particularly CeO2–ZrO2 (CZ) solid solutions are key ingredient in catalyst formulations for several applications due to the ability of ceria to easily cycling its oxidation state between Ce4+ and Ce3+. Ceria-based catalysts have a [...] Read more.
Ceria-based materials, and particularly CeO2–ZrO2 (CZ) solid solutions are key ingredient in catalyst formulations for several applications due to the ability of ceria to easily cycling its oxidation state between Ce4+ and Ce3+. Ceria-based catalysts have a great soot oxidation potential and the mechanism deeply relies on the degree of contact between CeO2 and carbon. In this study, carbon soot has been used as solid reductant to better understand the oxygen transfer ability of ceria–zirconia at low temperatures; the effect of different atmosphere and contact conditions has been investigated. The difference in the contact morphology between carbon soot and CZ particles is shown to strongly affect the oxygen transfer ability of ceria; in particular, increasing the carbon–ceria interfacial area, the reactivity of CZ lattice oxygen is significantly improved. In addition, with a higher degree of contact, the soot oxidation is less affected by the presence of NOx. The NO oxidation over CZ in the presence of soot has also been analyzed. The existence of a core/shell structure strongly enhances reactivity of interfacial oxygen species while affecting negatively NO oxidation characteristics. These findings are significant in the understanding of the redox chemistry of substituted ceria and help determining the role of active species in soot oxidation reaction as a function of the degree of contact between ceria and carbon. Full article
(This article belongs to the Special Issue Rare Earth-Doped Ceria Systems and Their Applications)
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10 pages, 3069 KiB  
Article
Morphology and Structural Stability of Bismuth-Gadolinium Co-Doped Ceria Electrolyte Nanopowders
by Grazia Accardo, Luca Spiridigliozzi, Gianfranco Dell’Agli, Sung Pil Yoon and Domenico Frattini
Inorganics 2019, 7(10), 118; https://doi.org/10.3390/inorganics7100118 - 28 Sep 2019
Cited by 17 | Viewed by 3236
Abstract
The reduction of the sintering temperature of doped ceria ceramics remains an open challenge for their real exploitation as electrolytes for intermediate temperature solid oxide fuel cell (IT-SOFCs) at the industrial level. In this work, we have used Bi (0.5 and 2 mol [...] Read more.
The reduction of the sintering temperature of doped ceria ceramics remains an open challenge for their real exploitation as electrolytes for intermediate temperature solid oxide fuel cell (IT-SOFCs) at the industrial level. In this work, we have used Bi (0.5 and 2 mol %) as the sintering aid for Gd (20 mol %)-doped ceria. Nano-sized powders of Bi/Gd co-doped ceria were easily synthesized via a simple and cheap sol-gel combustion synthesis. The obtained powders showed high sinterability and very good electrochemical properties. More importantly, even after prolonged annealing at 700 °C, both of the powders and of the sintered pellets, no trace of structural modifications, phase instabilities, or Bi segregation appeared. Therefore, the use of a small amount of Bi can be taken into account for preparing ceria-based ceramic electrolytes at low sintering temperatures. Full article
(This article belongs to the Special Issue Rare Earth-Doped Ceria Systems and Their Applications)
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13 pages, 3714 KiB  
Article
Local and Average Structure of Yb-Doped Ceria through Synchrotron and Neutron Pair Distribution Function
by Mauro Coduri, Dario Bozzetti, Stefano Checchia, Michela Brunelli and Marco Scavini
Inorganics 2019, 7(8), 102; https://doi.org/10.3390/inorganics7080102 - 18 Aug 2019
Cited by 3 | Viewed by 3466
Abstract
As transport properties of doped ceria electrolytes depend significantly on the nature of the dopant and the defectivity, the design of new materials and devices requires proper understanding of the defect structure. Among lanthanide dopants, Yb shows some peculiar characteristics that call for [...] Read more.
As transport properties of doped ceria electrolytes depend significantly on the nature of the dopant and the defectivity, the design of new materials and devices requires proper understanding of the defect structure. Among lanthanide dopants, Yb shows some peculiar characteristics that call for a possible different defect structure compared to Gd and Sm conventional dopants, which could be linked to its poorer performance. For this purpose, we combine synchrotron and neutron powder diffraction exploiting the Rietveld and Pair distribution Function. By increasing its concentration, Yb produces qualitatively the same structural distortions as other dopants, leading to a domain structure involving the progressive nucleation and growth of nanodomains with a Yb2O3-like (C-type) structure hosted in a fluorite CeO2 matrix. However, when it comes to growing the C-type nanodomains into a long-range phase, the transformation is less pronounced. At the same time, a stronger structural distortion occurs at the local scale, which is consistent with the segregation of a large amount of oxygen vacancies. The strong trapping of VOs by Yb3+ explains the poor performance of Yb-doped ceria with respect to conventional Sm-, Gd-, and Y-doped samples at equal temperature and dopant amount. Full article
(This article belongs to the Special Issue Rare Earth-Doped Ceria Systems and Their Applications)
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10 pages, 2398 KiB  
Article
Effect of the (Nd,Dy)-Double Doping on the Structural Properties of Ceria
by Cristina Artini, Lara Gigli, Maria Maddalena Carnasciali and Marcella Pani
Inorganics 2019, 7(8), 94; https://doi.org/10.3390/inorganics7080094 - 26 Jul 2019
Cited by 13 | Viewed by 3467
Abstract
The crystallographic properties of the Ce1−x(Nd0.63Dy0.37)xO2−x/2 system (0 ≤ x ≤ 0.6) were studied by means of synchrotron powder X-ray diffraction and compared to the ones of Sm-doped ceria. The aim [...] Read more.
The crystallographic properties of the Ce1−x(Nd0.63Dy0.37)xO2−x/2 system (0 ≤ x ≤ 0.6) were studied by means of synchrotron powder X-ray diffraction and compared to the ones of Sm-doped ceria. The aim of this work was to investigate the effect of substituting Sm3+ by a mixture of a smaller and a larger ion that ensures a more pronounced Ce4+/dopant size mismatch while having the same average ionic size as Sm3+. Two main findings came to light: (a) the compositional region of the CeO2-based solid solution widens up to x ranging between 0.4 and 0.5, and (b) the cell parameter is larger than the one of Sm-doped ceria at each composition. Both effects are expected to play a significant role on the ionic conductivity of the material. The results are discussed in terms of disorder and cation-vacancy association. Full article
(This article belongs to the Special Issue Rare Earth-Doped Ceria Systems and Their Applications)
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