On the Impact of the Degree of Fluorination on the ORR Limiting Processes within Iron Based Catalysts: A Model Study on Symmetrical Films of Barium Ferrate.

In this study, symmetrical films of BaFeO, BaFeOF and BaFeOF were synthesized and the oxygen uptake and conduction was investigated by high temperature impedance spectroscopy under an oxygen atmosphere. The data were analyzed on the basis of an impedance model designed for highly porous mixed ionic electronic conducting (MIEC) electrodes. Variable temperature X-ray diffraction experiments were utilized to estimate the stability window of the oxyfluoride compounds, which yielded a degradation temperature for BaFeOF of 590 °C and a decomposition temperature for BaFeOF of 710 °C. The impedance study revealed a significant change of the catalytic behavior in dependency of the fluorine content. BaFeO revealed a bulk-diffusion limited process, while BaFeOF appeared to exhibit a fast bulk diffusion and a utilization region δ larger than the electrode thickness L (8 μm). In contrast, BaFeOF showed very area specific resistances due to the lack of oxygen vacancies. The activation energy for the uptake and conduction process of oxygen was found to be 0.07/0.29 eV (temperature range-dependent), 0.33 eV and 0.67 eV for BaFeO, BaFeOF and BaFeOF, respectively.