The interaction of molecular oxygen on Lao terminated surfaces of La2NiO4

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

研究成果: ジャーナルへの寄稿記事

17 引用 (Scopus)

抄録

Rare-earth metal oxides with perovskite-type crystal structures are under consideration for use as air electrode materials for intermediate to high temperature electrochemical device applications. The surface chemistry of these materials plays a critical role in determining the kinetics of oxygen reduction and exchange reactions. Among various perovskite-structured oxides, certain members of the Ruddlesden-Popper series, e.g. La2NiO4, have been identified as significantly active for surface oxygen interactions. However, the challenge remains to be the identification of the structure and composition of active surfaces, as well as the influence of these factors on the mechanisms of surface exchange reactions. In this contribution, the changes in the electronic structure and the energetics of oxygen interactions on the surfaces of La2NiO4 are analysed using first principles calculations in the Density Functional Theory (DFT) formalism. As for the surface chemistry, LaO termination rather than NiO2 termination is presumed due to recent experimental evidence of the surfaces of various perovskite structured oxides after heat treatment in oxidizing environments being transition metal free. Our findings substantiate the fact that the LaO-terminated surface can indeed participate in the formation of surface superoxo species. Detailed charge transfer analyses revealed that it is possible for such a surface to be catalytically active owing to the enhanced electronic configurations on the neighbouring La sites to surface species. In addition, positively charged oxygen vacancies, relative to the crystal lattice, can act as active sites and catalyse the O-O bond cleavage.

元の言語英語
ページ(範囲)13113-13124
ページ数12
ジャーナルJournal of Materials Chemistry A
4
発行部数34
DOI
出版物ステータス出版済み - 1 1 2016

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Molecular oxygen
Perovskite
Oxides
Oxygen
Surface chemistry
Rare Earth Metals
Oxygen vacancies
Crystal lattices
Rare earths
Electronic structure
Transition metals
Density functional theory
Charge transfer
Ion exchange
Crystal structure
Heat treatment
Electrodes
Kinetics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

これを引用

The interaction of molecular oxygen on Lao terminated surfaces of La2NiO4 . / Akbay, Taner; Staykov, Aleksandar Tsekov; Druce, John William Richard; Tellez Lozano, Helena; Ishihara, Tatsumi; Kilner, John A.

:: Journal of Materials Chemistry A, 巻 4, 番号 34, 01.01.2016, p. 13113-13124.

研究成果: ジャーナルへの寄稿記事

Akbay, Taner ; Staykov, Aleksandar Tsekov ; Druce, John William Richard ; Tellez Lozano, Helena ; Ishihara, Tatsumi ; Kilner, John A. / The interaction of molecular oxygen on Lao terminated surfaces of La2NiO4 :: Journal of Materials Chemistry A. 2016 ; 巻 4, 番号 34. pp. 13113-13124.
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abstract = "Rare-earth metal oxides with perovskite-type crystal structures are under consideration for use as air electrode materials for intermediate to high temperature electrochemical device applications. The surface chemistry of these materials plays a critical role in determining the kinetics of oxygen reduction and exchange reactions. Among various perovskite-structured oxides, certain members of the Ruddlesden-Popper series, e.g. La2NiO4, have been identified as significantly active for surface oxygen interactions. However, the challenge remains to be the identification of the structure and composition of active surfaces, as well as the influence of these factors on the mechanisms of surface exchange reactions. In this contribution, the changes in the electronic structure and the energetics of oxygen interactions on the surfaces of La2NiO4 are analysed using first principles calculations in the Density Functional Theory (DFT) formalism. As for the surface chemistry, LaO termination rather than NiO2 termination is presumed due to recent experimental evidence of the surfaces of various perovskite structured oxides after heat treatment in oxidizing environments being transition metal free. Our findings substantiate the fact that the LaO-terminated surface can indeed participate in the formation of surface superoxo species. Detailed charge transfer analyses revealed that it is possible for such a surface to be catalytically active owing to the enhanced electronic configurations on the neighbouring La sites to surface species. In addition, positively charged oxygen vacancies, relative to the crystal lattice, can act as active sites and catalyse the O-O bond cleavage.",
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