Effect of the rare earth in the perovskite-type mixed oxides AMnO3 (A = Y, La, Pr, Sm, Dy) as catalysts in methanol oxidation

The effect of the rare earth in the perovskite-type mixed oxides AMnO(3) (A = Y, La, Pr, Sm, Dy) on catalytic properties in methanol oxidation was investigated in this work. The perovskites were prepared by reactive grinding in order to enhance the specific surface area in comparison with other classical synthesis procedures. These catalysts were characterized by N-2 adsorption, X-ray diffraction, H-2 temperature-programmed reduction (TPR-H-2), O-2-, CH3OH- and CO2-temperature-programmed desorption (TPD). The activity of the five catalysts under study in the methanol oxidation reaction was evaluated. The behaviour of the alpha-O-2 from the surface of the perovskite was strongly related to the nature of the A-site cation and particularly to its electronegativity but also to its density. Concerning the beta-O-2 from the bulk, the rare earth only induces an indirect effect notably due to structural modifications. As suggested in a previous study, the activity in methanol oxidation was directly linked with the surface oxygen density. Under an excess of alpha-oxygen, the reaction intermediate was found to be a monodentate carbonate that decomposes into CO2. The stability of monodentate carbonates was also found to be related to the electronegativity of the rare earth during both CH3OH- and CO2-temperature-programmed desorption. However, as soon as a lack of alpha-oxygen was observed in the structure, the dominant reaction intermediate was a bidentate carbonate that induces a consumption of anion vacancies in spite of the production of CO2. Nevertheless, the accumulation of these carbonates leads to a decrease in the oxidation rate since their desorption requires high temperatures. (c) 2008 Published by Elsevier Inc.