Activity and Thermal Aging Stability of La1-xSrxMnO3 (x = 0.0, 0.3, 0.5, 0.7) and Ir/La1-xSrxMnO3 Catalysts for CO Oxidation with Excess O2.

The catalytic oxidation of CO is probably the most investigated reaction in the literature, for decades, because of its extended environmental and fundamental importance. In this paper, the oxidation of CO on La1-xSrxMnO3 perovskites (LSMx), either unloaded or loaded with dispersed Ir nanoparticles (Ir/LSMx), was studied in the temperature range 100-450 °C under excess O2 conditions (1% CO + 5% O2). The perovskites, of the type La1-xSrxMnO3 (x = 0.0, 0.3, 0.5 and 0.7), were prepared by the coprecipitation method. The physicochemical and structural properties of both the LSMx and the homologous Ir/LSMx catalysts were evaluated by various techniques (XRD, N2 sorption-desorption by BET-BJH, H2-TPR and H2-Chem), in order to better understand the structure-activity-stability correlations. The effect of preoxidation/prereduction/aging of the catalysts on their activity and stability was also investigated. Results revealed that both LSMx and Ir/LSMx are effective for CO oxidation, with the latter being superior to the former. In both series of materials, increasing the substitution of La by Sr in the composition of the perovskite resulted to a gradual suppression of their CO oxidation activity when these were prereduced; the opposite was true for preoxidized samples. Inverse hysteresis phenomena in activity were observed during heating/cooling cycles on the prereduced Ir/LSMx catalysts with the loop amplitude narrowing with increasing Sr-content in LSMx. Oxidative thermal sintering experiments at high temperatures revealed excellent antisintering behavior of Ir nanoparticles supported on LSMx, resulting from perovskite's favorable antisintering properties of high oxygen storage capacity and surface oxygen vacancies.

Defect Chemistry and Chemical Looping Performance of La1-xMxMnO3 (M = Sr, Ca, (x = 0-0.5)) Perovskites.

La1-xMxMnO3 (M = Sr, Ca, (x = 0-0.5)) materials of the perovskite structure are synthesized by a co-precipitation method. They are subsequently investigated for their performance in a chemical looping process (fuel CH4) using thermogravimetric analysis with simultaneous reaction. The goal of this work is to determine the relation between the defect chemistry of the materials and their behavior in chemical looping processes. A defect model is proposed that provides an explanation of the dependency of the Oxygen Transfer Capacity and of the CO2/CO selectivity on composition. It appeared that the fuel may react with various types of oxygen available within the materials, generated by different mechanisms. The relative amounts of each oxygen type determine the CO2/CO selectivity and depend on the material composition as well as on the partial pressure of oxygen used for regenerating the materials.