Oxygen exchange and mechanism of oxygen intake by complex oxides with a swedenborgite structure

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Abstract

The kinetics of oxygen sorption from air by Y0.8Ca0.2BaCo4-xFexO7+δ (x = 0, 1) is studied by nonisothermal thermogravimetric measurements. The activation energy is calculated by model-free methods of Friedman, Starink and Vyazovkin. The master plot and Coates–Redfern methods are applied to determine the mechanism of oxygen intake. The results show the activation energies and frequency factors are 189 and 197 kJ mol–1 and 4.7 × 1013 and 2.3 × 1014 min–1 in Y0.8Ca0.2BaCo4O7+δ and Y0.8Ca0.2BaCo3FeO7+δ, respectively. The arguments are given in proof of oxygen sorption determined by the volume random nucleation and growth of the oxygen-rich nuclei.

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About the authors

D. I. Turkin

Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences

Author for correspondence.
Email: turkin@ihim.uran.ru
Russian Federation, 620077 Ekaterinburg

O. G. Reznitskikh

Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences

Email: turkin@ihim.uran.ru
Russian Federation, 620077 Ekaterinburg

V. L. Kozhevnikov

Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences

Email: turkin@ihim.uran.ru

Academician of the RAS

Russian Federation, 620077 Ekaterinburg

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2. Fig. 1. X-ray diffraction spectra of Y0.8Ca0.2BaCo4O7+δ and Y0.8Ca0.2BaCo3FeO7+δ samples for oxygen-depleted (a, b) and oxygen-enriched (c, d) phases along with the results of full-profile analysis (space group P63mc); the insets show enlarged fragments of diffraction patterns in the region of the main peaks of the hexagonal structure without visible traces of structural distortions.

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3. Fig. 2. Dependences of the refined structural parameters at room temperature of the YBaCo4O7+δ (YBC), Y0.8Ca0.2BaCo4O7+δ (YCBC) and Y0.8Ca0.2BaCo3FeO7+δ (YCBCF) samples after heat treatment in Ar at 650°C and subsequent cooling in air (a)–(d); sketch of the crystal structure of swedenborgite (d): tetrahedra of the crystallographic kagome and trigonal layers are shown in blue and green, respectively.

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4. Fig. 3. Thermograms of oxygen absorption by oxides Y0.8Ca0.2BaCo4O7+δ (a) and Y0.8Ca0.2BaCo3FeO7+δ (b) upon cooling in air.

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5. Fig. 4. Application of the Friedman (a), Starinka (b) and Vyazovkin (c) methods to determine the activation energy and the obtained dependences E(α) (d).

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6. Fig. 5. Kinetic compensation effect for Y0.8Ca0.2BaCo4O7+d and Y0.8Ca0.2BaCo3FeO7+d samples.

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7. Fig. 6. Theoretical (solid lines) and experimental (dots) dependences of the ratio g(α)/g(0.5) of the degree of transformation α for the samples Y0.8Ca0.2BaCo4O7+d and Y0.8Ca0.2BaCo3FeO7+d. The line designations on the graphs correspond to the reaction models from Table 1.

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