101. Tuning the Pr valence state to design high oxygen mobility, redox and transport properties in the CeO2-ZrO2-PrOx phase diagram
- Author
-
Philippe Vernoux, Jean-Marc Bassat, Vincent Frizon, Julien Hernandez, Alain Demourgues, Michaël Pollet, K. Pajot, Etienne Durand, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solvay (France), PSA Peugeot - Citroën (PSA), PSA Peugeot Citroën (PSA), and The authors acknowledge the PSA and SOLVAY companies for financial support.
- Subjects
Valence (chemistry) ,Materials science ,PROX ,Thermodynamics ,02 engineering and technology ,[CHIM.MATE]Chemical Sciences/Material chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,7. Clean energy ,Redox ,Magnetic susceptibility ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,General Energy ,High oxygen ,13. Climate action ,Physical and Theoretical Chemistry ,0210 nano-technology ,Phase diagram - Abstract
International audience; The preparation and characterization of pure fluorite-type phases allowed exploring the CeO2–ZrO2–PrOx (CZP) phase diagram. On the basis of magnetic susceptibility measurements, the Pr4+/Pr3+ molar ratio of several oxides annealed at T = 700 °C under air was determined; the higher the Zr content, the lower the Pr4+ concentration. Thermogravimetric analysis and temperature-programmed reduction measurements showed various Pr and Ce reduction steps. The Pr4+ reduction starts at T = 250 °C and is maximum around T = 400 °C. For the most reducible compositions, which exhibit the lowest Zr content and the highest Pr rate, the reduction phenomena strongly depend on the Pr/Ce molar ratio. As a remarkable result, Pr and Ce reductions can simultaneously take place at lower temperature (T > 430 °C) than for oxides of the CeO2–ZrO2 solid solution evidencing that the increase of Pr content also allows enhancing the reducibility of Ce4+ at low temperature. On the basis of a discussion taking into account the probability of oxygen surroundings in disordered fluorite networks and the rate of oxygen released in materials after the first reduction step performed at T < 500 °C, a mapping of the most probable labile oxygen sites in the CZP phase diagram is proposed. In particular, it is shown that for the oxides containing 10 atom % Zr, the most labile oxygen site should be systematically coordinated with one Zr atom, one Ce, and two Pr atoms. In the same series (10 atom % Zr), the electronic transport properties allowed showing semiconducting behavior with a strong increase of the total conductivity as the Pr content increases. On the basis of the thermal variation of the Seebeck coefficient, these phenomena are associated with hopping of electrons and holes, involving intra-atomic charge transfers, which depend on the reduction temperature of Pr4+ ions under air. Finally, the oxygen mobility strongly increases with the Pr content in this series. The oxygen tracer self-diffusion coefficient D* has been estimated by two independent measurements, and the best value is around 10–8 cm2/s at T = 400 °C for the Ce0.45Zr0.1Pr0.45O2–x composition, which is quite high in this temperature range. These fundamental properties of CZP phases design very promising new materials like automotive exhaust catalysts, gas sensors, electrolytes, or oxygen electrodes for solid oxide fuel cells.
- Published
- 2019
- Full Text
- View/download PDF