Oxygen Activation and Dissociation on Transition Metal Free Perovskite Surfaces

Aleksandar Tsekov Staykov, Helena Tellez Lozano, Taner Akbay, John William Richard Druce, Tatsumi Ishihara, John Kilner

研究成果: ジャーナルへの寄稿記事

29 引用 (Scopus)

抄録

Density functional theory and low energy ion scattering spectroscopy were applied to study the mechanism of oxygen dissociation on the SrO-terminated surfaces of strontium titanate (SrTiO3) and iron-doped strontium titanate (SrTi1-xFexO). Our study reveals that while O2 dissociation is not favored on the SrO-terminated perovskite surface, oxygen vacancies can act as active sites and catalyze the O-O bond cleavage. Electron transfer from lattice oxygen atoms to the O2 molecule, mediated by the subsurface transition metal cations, plays an important role in the resulting formation of surface superoxo species. The O2 molecule dissociates to produce oxygen ions, which are incorporated into the perovskite lattice, and highly active oxygen radicals on the perovskite surface, which further recombine to O2 molecules. Our focus on the SrO-terminated surface, rather than the TiO2 layer, which is presumed to be more catalytically active, was driven by experimental observation using low energy ion scattering spectroscopy, which reveals that the surface of SrTiO3 after high temperature heat treatment is SrO-terminated, and hence this is the surface that is technologically relevant for devices such as solid oxide fuel cells (SOFCs). Our study demonstrates that although the more active BO2-perovskite layer is not exposed at the gas-solid interface, the SrO-terminated surfaces also actively participate in oxygen exchange reaction.

元の言語英語
ページ(範囲)8273-8281
ページ数9
ジャーナルChemistry of Materials
27
発行部数24
DOI
出版物ステータス出版済み - 12 22 2015

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Perovskite
Transition metals
Chemical activation
Oxygen
Strontium
Ions
Molecules
Reactive Oxygen Species
Spectroscopy
Scattering
perovskite
Oxygen vacancies
Solid oxide fuel cells (SOFC)
Density functional theory
Cations
Iron
Gases
Positive ions
Heat treatment
Atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

これを引用

Oxygen Activation and Dissociation on Transition Metal Free Perovskite Surfaces. / Staykov, Aleksandar Tsekov; Tellez Lozano, Helena; Akbay, Taner; Druce, John William Richard; Ishihara, Tatsumi; Kilner, John.

:: Chemistry of Materials, 巻 27, 番号 24, 22.12.2015, p. 8273-8281.

研究成果: ジャーナルへの寄稿記事

Staykov, Aleksandar Tsekov ; Tellez Lozano, Helena ; Akbay, Taner ; Druce, John William Richard ; Ishihara, Tatsumi ; Kilner, John. / Oxygen Activation and Dissociation on Transition Metal Free Perovskite Surfaces. :: Chemistry of Materials. 2015 ; 巻 27, 番号 24. pp. 8273-8281.
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abstract = "Density functional theory and low energy ion scattering spectroscopy were applied to study the mechanism of oxygen dissociation on the SrO-terminated surfaces of strontium titanate (SrTiO3) and iron-doped strontium titanate (SrTi1-xFexO3Δ). Our study reveals that while O2 dissociation is not favored on the SrO-terminated perovskite surface, oxygen vacancies can act as active sites and catalyze the O-O bond cleavage. Electron transfer from lattice oxygen atoms to the O2 molecule, mediated by the subsurface transition metal cations, plays an important role in the resulting formation of surface superoxo species. The O2 molecule dissociates to produce oxygen ions, which are incorporated into the perovskite lattice, and highly active oxygen radicals on the perovskite surface, which further recombine to O2 molecules. Our focus on the SrO-terminated surface, rather than the TiO2 layer, which is presumed to be more catalytically active, was driven by experimental observation using low energy ion scattering spectroscopy, which reveals that the surface of SrTiO3 after high temperature heat treatment is SrO-terminated, and hence this is the surface that is technologically relevant for devices such as solid oxide fuel cells (SOFCs). Our study demonstrates that although the more active BO2-perovskite layer is not exposed at the gas-solid interface, the SrO-terminated surfaces also actively participate in oxygen exchange reaction.",
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