Determination of Kinetic Parameters and Identification of the Rate-Determining Steps in the Oxygen Exchange Process for LaNi0.6Fe0.4O3-δ.

The mixed ionic and electronic oxide LaNi0.6Fe0.4O3-δ (LNF) is a promising ceramic cathode material for solid oxide fuel cells. Since the reaction rate of oxygen interaction with the cathode material is extremely important, the present work considers the oxygen exchange mechanism between O2 and LNF oxide. The kinetic dependence of the oxygen/oxide interaction has been determined by two isotopic methods using 18O-labelled oxygen. The application of the isotope exchange with the gas phase equilibrium (IE-GPE) and the pulsed isotope exchange (PIE) has provided information over a wide range of temperatures (350-800 °C) and oxygen pressures (10-200 mbar), as each method has different applicability limits. Applying mathematical models to treat the kinetic relationships, the oxygen exchange rate (rH, atom × cm-2 × s-1) and the diffusion coefficient (D, cm2/s) were calculated. The values of rH and D depend on both temperature and oxygen pressure. The activation energy of the surface exchange rate is 0.73 ± 0.05 eV for the PIE method at 200 mbar, and 0.48 ± 0.02 eV for the IE-GPE method at 10-20 mbar; for the diffusion coefficient, the activation energy equals 0.62 ± 0.01 eV at 10-20 mbar for the IE-GPE method. Differences in the mechanism of oxygen exchange and diffusion on dense and powder samples are observed due to the different microstructure and surface morphology of the samples. The influence of oxygen pressure on the ratio of contributions of different exchange types to the total oxygen exchange rate is demonstrated. For the first time, the rate-determining step in the oxygen exchange process for LNF material has been identified. This paper discusses the reasons for the difference in the mechanisms of oxygen exchange and diffusion.

Correlation between structure, surface defect chemistry and 18O/16O exchange for La2Mo2O9 and La2(MoO4)3.

The La2Mo2O9 and La2(MoO4)3 powders were synthesized using a solid-state reaction method and used to prepare dense ceramics. X-ray photoelectron spectroscopy was used to study the chemical composition and charge numbers of the elements in the subsurface area of dense ceramics of lanthanum molybdates. The spectra were measured under an ultra-high vacuum of 7 × 10-11 atm at 30 °C and 600 °C, and under an oxygen atmosphere at 2 × 10-3 atm at 600 °C and 825 °C. High resolution spectra for La 3d, Mo 3d and O 1s states were obtained and analyzed. The kinetics of oxygen exchange were considered in the framework of a two-step model including the consecutive steps of dissociative adsorption and the incorporation of oxygen. The oxygen adsorption (ra) and incorporation (ri) rates were calculated. Correlations between the oxide surface defect chemistry and the rates of individual oxygen-exchange steps were discussed.

Oxygen surface exchange and diffusion in Pr1.75Sr0.25Ni0.75Co0.25O4±Î´.

Oxygen surface exchange and diffusion in Pr1.75Sr0.25Ni0.75Co0.25O4±Î´ have been investigated using two methods: pulsed isotope exchange (PIE) and oxygen isotope exchange with gas phase equilibration (IE GPE). Oxygen surface exchange kinetics is considered in the framework of two-step models including two consecutive stages: dissociative adsorption of oxygen and incorporation of oxygen adatoms into the crystal lattice. The rates of oxygen heterogeneous exchange (rH) as well as the rates of dissociative adsorption (ra) and oxygen incorporation (ri) have been calculated. The applicability of the two-step model is discussed based on the concept of a novel two-step mechanism with distributed rates of dissociative adsorption and incorporation of oxygen. It is shown that the two-step model can be applicable for the description of oxygen exchange kinetics in Pr1.75Sr0.25Ni0.75Co0.25O4±Î´ only at temperatures below 750 °C. Above this temperature, only the statistical model with distributed rates can be used. At low temperatures (<750 °C), the oxygen incorporation rate is found to be smaller than the rate of oxygen dissociative adsorption. Thus, under these experimental conditions the stage of oxygen incorporation is considered to be rate-determining. When increasing the temperature, the difference between ra and ri decreases and the stages become competing. The oxygen isotope exchange kinetic profiles obtained using the IE GPE method are found to be complicated and include a surface exchange stage as well as at least two diffusion relaxation processes. The reasons for the existence of these two processes are discussed.