Consistent interpretation of isotope and chemical oxygen exchange relaxation kinetics in SrFe0.85Mo0.15O3-δ ferrite.

This paper is devoted to the study of phase composition and kinetic and thermodynamic characteristics of Mo-doped strontium ferrite SrFe0.85Mo0.15O3-δ (SFM15) under oxygen-conducting membrane working conditions. Single-phase SFM15 with a cubic Pm3̄m structure was synthesized using a ceramic method. It was shown that the molybdenum introduction stabilizes the perovskite cubic structure over a wide range of oxygen pressures and temperatures, preventing the bulk phase transition at high temperatures. Oxygen exchange constants, diffusion coefficients and activation energy of oxygen exchange were obtained using oxygen relaxation and isotopic exchange techniques, and the obtained values are consistent with known literature data. It was shown that the surface reaction rates obtained using chemical and tracer relaxation methods are quantitatively comparable with each other, despite significantly different experimental conditions. This result not only confirms the reliability of the data obtained by independent methods, but also allows one to expand the area of physical conditions for studying the kinetics of oxygen transfer where another method has technical or methodological limitations.

The Brønsted-Evans-Polanyi relationship in oxygen exchange of fuel cell cathode material SrCo0.9Ta0.1O3-δ with the gas phase.

Perovskite related oxides ABO3-δ exhibiting mixed ionic-electronic conductivity (MIEC) possess large deviations from the oxygen stoichiometry. When providing excellent application potential, this feature also makes it very difficult to study the reaction mechanism between such oxides and molecular oxygen, also known as the oxygen reduction reaction. The complexity of the theoretical interpretation of kinetic experiments originates from the significant dependence of the kinetic and equilibrium properties of MIEC oxides on δ. It is proposed to consider such grossly nonstoichiometric oxides having different oxygen nonstoichiometry as chemical homologues participating in the oxygen exchange reaction and forming a series continuous in δ. The continuous homologous series approach is considered using the example of SrCo0.9Ta0.1O3-δ, an SOFC cathode material. The equilibrium and kinetic properties of the oxide were studied by new methods of oxygen partial pressure relaxation and oxygen release. Linear free-energy relationships have been discovered in the homologous series: thermodynamic and kinetic enthalpy-entropy compensations, as well as the Brønsted-Evans-Polanyi relation. A relationship has been established between the change in the observed LFERs and the morphotropic phase transition in the oxide.

Nonstoichiometric oxides as a continuous homologous series: linear free-energy relationship in oxygen exchange.

A novel methodology for the analysis of oxygen exchange in practically important nonstoichiometric oxides with mixed ionic electronic conductivity (MIEC) is suggested. It is based on the fact that the kinetic and thermodynamic properties of such oxides vary continuously with oxygen stoichiometry. This allows MIEC oxides to be considered as a homologous series, with the difference that traditional series are discrete in their chemical composition whereas MIEC oxides are continuous in oxygen stoichiometry. Analysis of the relations between Gibbs energies of reactions and activation barriers traditionally performed for homologous series can be useful in studies of oxygen exchange in MIEC oxides. To demonstrate the approach, thermodynamic and oxygen-exchange kinetics parameters are measured as functions of oxygen nonstoichiometry δ for two perovskites, SrCo0.8Fe0.2O3-δ and SrFeO3-δ, having metal-like and p-type semiconducting conductivities, respectively. Both oxides are shown to obey linear free energy relationships of the Brønsted-Evans-Polanyi form in spite of their different types of electronic structures. The results open up new possibilities for understanding the mechanism of the rate determining step of oxygen exchange in MIEC oxides.

Oxygen release technique as a method for the determination of "δ-pO2-T" diagrams for MIEC oxides.

A new approach to the determination of oxygen nonstoichiometry (δ) of MIEC oxides as a continuous function of pO2 at high temperatures was developed. The description of the model allowing one to distinguish the contribution of oxygen released from the samples to the partial pressure of oxygen at the outlet of the continuous-flow fixed-bed reactor after the stepwise change of the oxygen partial pressure of inlet gas from 0.2 to 10(-5) atm and to calculate the dependence of δ on pO2 is presented. The criterion for assessing the achievement of quasi equilibrium release of oxygen from the MIEC oxides is proposed. The adequacy of the method was confirmed by comparing the obtained and published data for well-studied SrCo0.8Fe0.2O3-δ and SrFeO3-δ MIEC oxides.