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Enthalpy increments and redox thermodynamics of SrFeO3−δ

Published online by Cambridge University Press:  30 August 2019

Vladimir Sereda*
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia; and Department of Solid State Electrochemistry, Institute of High-Temperature Electrochemistry UB RAS, Yekaterinburg 620137, Russia
Anton Sednev
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia; and Department of Solid State Electrochemistry, Institute of High-Temperature Electrochemistry UB RAS, Yekaterinburg 620137, Russia
Dmitry Tsvetkov
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia
Andrey Zuev
Affiliation:
Department of Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Ural Federal University, Yekaterinburg 620002, Russia
*Corresponding
a)Address all correspondence to this author. e-mail: vladimir.sereda@urfu.ru
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Abstract

Enthalpy increments, $\Delta _{298}^T{H^0}$, for highly nonstoichiometric SrFeO3−δ (δ = 0.18–0.41) were obtained between 373 and 1273 K in air using drop calorimetry. The analysis of the $\Delta _{298}^T{H^0}\left( T \right)$ dependence at lower temperatures allowed evaluating the enthalpy of tetragonal to cubic ${{I4} / {mmm}} \,{\tf="TeX CM Bold Maths Symbols"\char33}\, Pm\bar{3}m$ phase transition at 560 K, 1.57 kJ/mol, and the Maier–Kelley function for $\Delta _{298}^T{H^0}\left( T \right)$ of tetragonal SrFeO3−δ (space group ${{I4} / {mmm}}$). Combined investigation of oxygen nonstoichiometry $\bolddelta \left( T \right)$ dependence, measured by thermogravimetry, and higher-temperature $\Delta _{298}^T{H^0}\left( T \right)$ of cubic SrFeO3−δ (space group $Pm\bar{3}m$) yielded the temperature-dependent reduction (oxygen release) enthalpy, $\Delta H_{{\rm{red}}}^{\rm{0}}$. Calorimetrically-determined $\Delta H_{{\rm{red}}}^{\rm{0}}$ of SrFeO3−δ increases from 65 ± 7 kJ/mol O at 873–973 K to 84 ± 7 kJ/mol O at 1073–1273 K, which may indicate that the short-range vacancy ordering in SrFeO3−δ is hampered at higher temperatures.

Type
Invited Paper
Copyright
Copyright © Materials Research Society 2019 

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References

Takeda, Y., Kanno, K., Takada, T., Yamamoto, O., Takano, M., Nakayama, N., and Bando, Y.: Phase relation in the oxygen nonstoichiometric system, SrFeOx (2.5 ≤ x ≤ 3.0). J. Solid State Chem. 63, 237 (1986).CrossRefGoogle Scholar
Mizusaki, J., Okayasu, M., Yamauchi, S., and Fueki, K.: Nonstoichiometry and phase relationship of the SrFeO2.5–SrFeO3 system at high temperature. J. Solid State Chem. 99, 166 (1992).CrossRefGoogle Scholar
Hodges, J.P., Short, S., Jorgensen, J.D., Xiong, X., Dabrowski, B., Mini, S.M., and Kimball, C.W.: Evolution of oxygen-vacancy ordered crystal structures in the perovskite series SrnFenO3n−1 (n = 2, 4, 8, and ∞), and the relationship to electronic and magnetic properties. J. Solid State Chem. 151, 190 (2000).CrossRefGoogle Scholar
Schmidt, M. and Campbell, S.J.: In situ neutron diffraction study (300–1273 K) of non-stoichiometric strontium ferrite SrFeOx. J. Phys. Chem. Solids 63, 2085 (2002).CrossRefGoogle Scholar
Jacobson, A.J.: Materials for solid oxide fuel cells. Chem. Mater. 22, 660 (2010).CrossRefGoogle Scholar
Sunarso, J., Baumann, S., Serra, J.M., Meulenberg, W.A., Liu, S., Lin, Y.S., and Diniz da Costa, J.C.: Mixed ionic–electronic conducting (MIEC) ceramic-based membranes for oxygen separation. J. Membr. Sci. 320, 13 (2008).CrossRefGoogle Scholar
Bakken, E., Stølen, S., Norby, T., Glenne, R., and Budd, M.: Redox energetics of SrFeO3−δ—A coulometric titration study. Solid State Ionics 167, 367 (2004).CrossRefGoogle Scholar
Cheng, J., Navrotsky, A., Zhou, X-D., and Anderson, H.U.: Thermochemistry of La1−xSrxFeO3−δ solid solutions (0.0 ≤ x ≤ 1.0, 0.0 ≤ δ ≤ 0.5). Chem. Mater. 17, 2197 (2005).CrossRefGoogle Scholar
Haavik, C., Atake, T., Kawaji, H., and Stølen, S.: On the entropic contribution to the redox energetics of SrFeO3−δ. Phys. Chem. Chem. Phys. 3, 3863 (2001).CrossRefGoogle Scholar
Haavik, C., Atake, T., and Stølen, S.: On the enthalpic contribution to the redox energetics of SrFeO3−δ. Phys. Chem. Chem. Phys. 4, 1082 (2002).CrossRefGoogle Scholar
Haavik, C., Bakken, E., Norby, T., Stølen, S., Atake, T., and Tojo, T.: Heat capacity of SrFeO3−δ; δ = 0.50, 0.25 and 0.15—Configurational entropy of structural entities in grossly non-stoichiometric oxides. Dalton Trans. 3, 361 (2003).CrossRefGoogle Scholar
Jia, T., Zeng, Z., Lin, H.Q., Duan, Y., and Ohodnicki, P.: First-principles study on the electronic, optical and thermodynamic properties of ABO3 (A = La,Sr, B = Fe,Co) perovskites. RSC Adv. 7, 38798 (2017).CrossRefGoogle Scholar
Holt, A., Norby, T., and Glenne, R.: Defects and transport in SrFe1−xCoxO3−δ. Ionics 5, 434 (1999).CrossRefGoogle Scholar
Diethelm, S., Closset, A., Van Herle, J., and Nisancioglu, K.: Oxygen transport and nonstoichiometry in SrFeO3−δ. Electrochemistry 68, 444 (2000).Google Scholar
Vashuk, V.V., Kokhanovskii, L.V., and Yushkevich, I.I.: Electrical conductivity and oxygen stoichiometry of SrFeO3−δ. Inorg. Mater. 36, 79 (2000).CrossRefGoogle Scholar
Patrakeev, M.V., Shilova, J.A., Mitberg, E.B., Lakhtin, A.A., Leonidov, I.A., and Kozhevnikov, V.L.: Oxygen intercalation in strontium ferrite: Evolution of thermodynamics and electron transport properties. In New Trends in Intercalation Compounds for Energy Storage, Julien, C., Pereira-Ramos, J.P., and Momchilov, A., eds. (Springer, Dordrecht, The Netherlands, 2002); p. 565.CrossRefGoogle Scholar
Starkov, I., Bychkov, S., Matvienko, A., and Nemudry, A.: Oxygen release technique as a method for the determination of “δ–pO2–T” diagrams for MIEC oxides. Phys. Chem. Chem. Phys. 16, 5527 (2014).CrossRefGoogle ScholarPubMed
Merkulov, O.V., Naumovich, E.N., Patrakeev, M.V., Markov, A.A., Bouwmeester, H.J.M., Leonidov, I.A., and Kozhevnikov, V.L.: Oxygen nonstoichiometry and defect chemistry of perovskite-structured SrFe1−xMoxO3−δ solid solutions. Solid State Ionics 292, 116 (2016).CrossRefGoogle Scholar
Yoo, J., Yoo, C-Y., Yu, J-H., and Jacobson, A.J.: Determination of oxygen nonstoichiometry in SrFeO3−δ by solid-state Coulometric titration. J. Am. Ceram. Soc. 100, 2690 (2017).CrossRefGoogle Scholar
Vieten, J., Bulfin, B., Senholdt, M., Roeb, M., Sattler, C., and Schmücker, M.: Redox thermodynamics and phase composition in the system SrFeO3−δ–SrMnO3−δ. Solid State Ionics 308, 149 (2017).CrossRefGoogle Scholar
Sereda, V.V., Tsvetkov, D.S., Ivanov, I.L., and Zuev, A.Y.: Interplay between chemical strain, defects and ordering in Sr1−xLaxFeO3 materials. Acta Mater. 162, 33 (2019).CrossRefGoogle Scholar
Shomate, C.H.: A method for evaluating and correlating thermodynamic data. J. Phys. Chem. 58, 368 (1954).CrossRefGoogle Scholar
Ikeda, H., Nikata, S., Hirakawa, E., Tsuchida, A., and Miura, N.: Oxygen sorption/desorption behavior and crystal structural change for SrFeO3−δ. Chem. Eng. Sci. 147, 166 (2016).CrossRefGoogle Scholar
Mizusaki, J., Yoshihiro, M., Yamauchi, S., and Fueki, K.: Nonstoichiometry and defect structure of the perovskite-type oxides La1−xSrxFeO3−d. J. Solid State Chem. 58, 257 (1985).CrossRefGoogle Scholar
Zuev, A.Y. and Tsvetkov, D.S.: Conventional methods for measurements of chemo-mechanical coupling. In Electro-Chemo-Mechanics of Solids, Bishop, S.R., Perry, N.H., Marrocchelli, D., and Sheldon, B.W., eds. (Springer International Publishing, Cham, Switzerland, 2017); p. 5.CrossRefGoogle Scholar
Sereda, V.V., Tsvetkov, D.S., Sednev, A.L., Druzhinina, A.I., Malyshkin, D.A., and Zuev, A.Y.: Thermodynamics of Sr2NiMoO6 and Sr2CoMoO6 and their stability under reducing conditions. Phys. Chem. Chem. Phys. 20, 20108 (2018).CrossRefGoogle ScholarPubMed

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