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Mössbauer studies of the phase composition and microstructure of the La1-xCaxFeO3-y system as related to the reactivity of surface and bulk oxygen

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Abstract

The phase composition and microstructure of samples of the La1-xCaxFeO3-y system prepared via a ceramic route were characterized by Mössbauer spectroscopy. In all cases, iron was found in the 3+ state. The ordering of anion vacancies in the samples with the composition in the range of 0.8 > x ≥ 0.4, which corresponds to a microheterogeneous solid solution, generates new distorted octahedral and fivefold/tetrahedral sites revealed by two typical sextets. The disordering of this solid solution and small (10-100 Å) sizes of domains with a perovskite, braunmillerite or Grenier phase structure caused the appearance of a superparamagnetic doublet, which grows with the Ca content up to x = 0.8 but disappears in the sample of pure braunmillerite. The appearance of Fe cations in a distorted coordination correlates with the increased activity of the samples with a microheterogeneous structure in the CO catalytic oxidation and with their reducibility by H2.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia

    L.A. Isupova, I.S. Yakovleva & V.A. Sadykov

  2. Institute of Solid State Chemistry Kutateladze st., 18, Novosibirsk, 630090, Russia

    I.I. Gainutdinov & Yu.T. Pavlyukhin

Authors
  1. L.A. Isupova
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  2. I.S. Yakovleva
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  3. I.I. Gainutdinov
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  4. Yu.T. Pavlyukhin
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  5. V.A. Sadykov
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Isupova, L., Yakovleva, I., Gainutdinov, I. et al. Mössbauer studies of the phase composition and microstructure of the La1-xCaxFeO3-y system as related to the reactivity of surface and bulk oxygen. Reaction Kinetics and Catalysis Letters 81, 373–382 (2004). https://doi.org/10.1023/B:REAC.0000019446.25192.67

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  • DOI: https://doi.org/10.1023/B:REAC.0000019446.25192.67

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