XPS characterization of gamma-ray induced chemisorption of oxygen in lanthanum manganate (LaMnO3)

Catalysis of mixed oxide LaMnO3 was studied for the decomposition of hydrogen peroxide (H2O2). The catalyst was γ-irradiated in open petri dishes, vacuum, dry oxygen and moist oxygen. LaMnO3 irradiated in moist oxygen showed highest catalytic activity. X-ray photoelectron spectroscopic (XPS) studies were carried out to investigate the surface modifications occur ed during γ-irradiation of LaMnO3. No significant change in the surface was noticed in LaMnO3 irradiated in vacuum and dry oxygen. However, LaMnO3 irradiated in moist oxygen and in open petri dishes showed the reduction of transition metal (MN3= to Mn2=) which in turn leads to the formation of chemisorbed superoxide ions (O-2) and surface carbonate species (CO32-). The latter processes decreases the electrical conductivity by trapping the charge carriers. The hydrated electron generated by the radiolysis of moisture reduces the transition metal. A qualitative molecular orbital model has been proposed for the chemisorption of O2- on the reduced transition metal centers (Mn2+). (author) 14 refs.; 6 figs.; 2 tabs