Oxygen storage capability in Co- and Fe-containing perovskite-type oxides

Alicja Klimkowicz, Konrad Świerczek, Akito Takasaki, Bogdan Dabrowski

Research output: Contribution to journalArticle

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Abstract

In this paper we report on oxygen storage-related properties of selected Co- and Fe-containing perovskite-type oxides, and analyze their advantages and disadvantages in relation to the Mn-based, A-site ordered BaYMn2O5 + δ system. In particular, the crystal structure of reduced and oxidized Ln0.5A′0.5Co0.5Fe0.5O3 - δ (Ln: La, Sm; A′: Sr, Ba) and La0.6Sr0.4Co0.8Fe0.2O3 - δ is given, results of in situ XRD observation of the oxidation process of the reduced materials is presented, as well as oxygen storage capacity and kinetics measured on oxidation/reduction cycles in isothermal and non-isothermal conditions are reported. Rietveld refinement of the crystal structure carried out for reduced compounds revealed the presence of brownmillerite-type phase for La0.6Sr0.4Co0.2Fe0.8O2.42, La0.5Sr0.5Co0.5Fe0.5O2.53 and Sm0.5Sr0.5Co0.5Fe0.5O2.53. Upon oxidation these materials transform to perovskite-type phase. On the contrary, La0.5Ba0.5Co0.5Fe0.5O3 - δ and A-site cation ordered Sm0.5Ba0.5Co0.5Fe0.5O3 - δ possess the same crystal structure in the reduced and oxidized forms. What's more is that the oxidation process causes a significant decrease of the unit cell volume for each studied compound. Rapid in situ XRD studies (1 min scans), performed every 5 C during oxidation of the materials, allowed to observe ongoing structural changes. TG measurements revealed unusually low onset temperatures of oxidation, with reduced La0.5Sr0.5Co0.5Fe0.5O3 - δ oxidizing at about 40 C. Isothermal oxidation/reduction cycles measured with changing of the atmosphere between air and 5 vol.% H2 in Ar, performed in 400-600 C allowed to establish oxygen storage-related properties of the studied materials, and it was found that La0.5Sr0.5Co0.5Fe0.5O3 - δ shows enhanced kinetics of the reduction process, while for La0.6Sr0.4Co0.8Fe0.2O3 - δ the measured reversible oxygen storage capacity can exceed 4.2 wt.%, well above that of the BaYMn2O5 + δ system. While these results are very promising, the main drawback arises from a low stability of the considered Co- and Fe-containing oxides, especially in terms of their long-time performance.

Original languageEnglish
Pages (from-to)23-28
Number of pages6
JournalSolid State Ionics
Volume257
DOIs
Publication statusPublished - 2014 Apr 1

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Perovskite
Oxides
Oxygen
Oxidation
oxidation
oxides
oxygen
Crystal structure
crystal structure
Rietveld refinement
Kinetics
Cations
cycles
kinetics
Positive ions
perovskite
Air
cations
atmospheres
causes

Keywords

  • Chemical stability
  • Crystal structure
  • Oxygen storage materials (OSMs)
  • Perovskite oxides

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Chemistry(all)

Cite this

Oxygen storage capability in Co- and Fe-containing perovskite-type oxides. / Klimkowicz, Alicja; Świerczek, Konrad; Takasaki, Akito; Dabrowski, Bogdan.

In: Solid State Ionics, Vol. 257, 01.04.2014, p. 23-28.

Research output: Contribution to journalArticle

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abstract = "In this paper we report on oxygen storage-related properties of selected Co- and Fe-containing perovskite-type oxides, and analyze their advantages and disadvantages in relation to the Mn-based, A-site ordered BaYMn2O5 + δ system. In particular, the crystal structure of reduced and oxidized Ln0.5A′0.5Co0.5Fe0.5O3 - δ (Ln: La, Sm; A′: Sr, Ba) and La0.6Sr0.4Co0.8Fe0.2O3 - δ is given, results of in situ XRD observation of the oxidation process of the reduced materials is presented, as well as oxygen storage capacity and kinetics measured on oxidation/reduction cycles in isothermal and non-isothermal conditions are reported. Rietveld refinement of the crystal structure carried out for reduced compounds revealed the presence of brownmillerite-type phase for La0.6Sr0.4Co0.2Fe0.8O2.42, La0.5Sr0.5Co0.5Fe0.5O2.53 and Sm0.5Sr0.5Co0.5Fe0.5O2.53. Upon oxidation these materials transform to perovskite-type phase. On the contrary, La0.5Ba0.5Co0.5Fe0.5O3 - δ and A-site cation ordered Sm0.5Ba0.5Co0.5Fe0.5O3 - δ possess the same crystal structure in the reduced and oxidized forms. What's more is that the oxidation process causes a significant decrease of the unit cell volume for each studied compound. Rapid in situ XRD studies (1 min scans), performed every 5 C during oxidation of the materials, allowed to observe ongoing structural changes. TG measurements revealed unusually low onset temperatures of oxidation, with reduced La0.5Sr0.5Co0.5Fe0.5O3 - δ oxidizing at about 40 C. Isothermal oxidation/reduction cycles measured with changing of the atmosphere between air and 5 vol.{\%} H2 in Ar, performed in 400-600 C allowed to establish oxygen storage-related properties of the studied materials, and it was found that La0.5Sr0.5Co0.5Fe0.5O3 - δ shows enhanced kinetics of the reduction process, while for La0.6Sr0.4Co0.8Fe0.2O3 - δ the measured reversible oxygen storage capacity can exceed 4.2 wt.{\%}, well above that of the BaYMn2O5 + δ system. While these results are very promising, the main drawback arises from a low stability of the considered Co- and Fe-containing oxides, especially in terms of their long-time performance.",
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AU - Takasaki, Akito

AU - Dabrowski, Bogdan

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N2 - In this paper we report on oxygen storage-related properties of selected Co- and Fe-containing perovskite-type oxides, and analyze their advantages and disadvantages in relation to the Mn-based, A-site ordered BaYMn2O5 + δ system. In particular, the crystal structure of reduced and oxidized Ln0.5A′0.5Co0.5Fe0.5O3 - δ (Ln: La, Sm; A′: Sr, Ba) and La0.6Sr0.4Co0.8Fe0.2O3 - δ is given, results of in situ XRD observation of the oxidation process of the reduced materials is presented, as well as oxygen storage capacity and kinetics measured on oxidation/reduction cycles in isothermal and non-isothermal conditions are reported. Rietveld refinement of the crystal structure carried out for reduced compounds revealed the presence of brownmillerite-type phase for La0.6Sr0.4Co0.2Fe0.8O2.42, La0.5Sr0.5Co0.5Fe0.5O2.53 and Sm0.5Sr0.5Co0.5Fe0.5O2.53. Upon oxidation these materials transform to perovskite-type phase. On the contrary, La0.5Ba0.5Co0.5Fe0.5O3 - δ and A-site cation ordered Sm0.5Ba0.5Co0.5Fe0.5O3 - δ possess the same crystal structure in the reduced and oxidized forms. What's more is that the oxidation process causes a significant decrease of the unit cell volume for each studied compound. Rapid in situ XRD studies (1 min scans), performed every 5 C during oxidation of the materials, allowed to observe ongoing structural changes. TG measurements revealed unusually low onset temperatures of oxidation, with reduced La0.5Sr0.5Co0.5Fe0.5O3 - δ oxidizing at about 40 C. Isothermal oxidation/reduction cycles measured with changing of the atmosphere between air and 5 vol.% H2 in Ar, performed in 400-600 C allowed to establish oxygen storage-related properties of the studied materials, and it was found that La0.5Sr0.5Co0.5Fe0.5O3 - δ shows enhanced kinetics of the reduction process, while for La0.6Sr0.4Co0.8Fe0.2O3 - δ the measured reversible oxygen storage capacity can exceed 4.2 wt.%, well above that of the BaYMn2O5 + δ system. While these results are very promising, the main drawback arises from a low stability of the considered Co- and Fe-containing oxides, especially in terms of their long-time performance.

AB - In this paper we report on oxygen storage-related properties of selected Co- and Fe-containing perovskite-type oxides, and analyze their advantages and disadvantages in relation to the Mn-based, A-site ordered BaYMn2O5 + δ system. In particular, the crystal structure of reduced and oxidized Ln0.5A′0.5Co0.5Fe0.5O3 - δ (Ln: La, Sm; A′: Sr, Ba) and La0.6Sr0.4Co0.8Fe0.2O3 - δ is given, results of in situ XRD observation of the oxidation process of the reduced materials is presented, as well as oxygen storage capacity and kinetics measured on oxidation/reduction cycles in isothermal and non-isothermal conditions are reported. Rietveld refinement of the crystal structure carried out for reduced compounds revealed the presence of brownmillerite-type phase for La0.6Sr0.4Co0.2Fe0.8O2.42, La0.5Sr0.5Co0.5Fe0.5O2.53 and Sm0.5Sr0.5Co0.5Fe0.5O2.53. Upon oxidation these materials transform to perovskite-type phase. On the contrary, La0.5Ba0.5Co0.5Fe0.5O3 - δ and A-site cation ordered Sm0.5Ba0.5Co0.5Fe0.5O3 - δ possess the same crystal structure in the reduced and oxidized forms. What's more is that the oxidation process causes a significant decrease of the unit cell volume for each studied compound. Rapid in situ XRD studies (1 min scans), performed every 5 C during oxidation of the materials, allowed to observe ongoing structural changes. TG measurements revealed unusually low onset temperatures of oxidation, with reduced La0.5Sr0.5Co0.5Fe0.5O3 - δ oxidizing at about 40 C. Isothermal oxidation/reduction cycles measured with changing of the atmosphere between air and 5 vol.% H2 in Ar, performed in 400-600 C allowed to establish oxygen storage-related properties of the studied materials, and it was found that La0.5Sr0.5Co0.5Fe0.5O3 - δ shows enhanced kinetics of the reduction process, while for La0.6Sr0.4Co0.8Fe0.2O3 - δ the measured reversible oxygen storage capacity can exceed 4.2 wt.%, well above that of the BaYMn2O5 + δ system. While these results are very promising, the main drawback arises from a low stability of the considered Co- and Fe-containing oxides, especially in terms of their long-time performance.

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