The Influence of the Chemical Potential on Defects and Function of Perovskites in Catalysis

A Sm-deficient Sm_0.96MnO₃ perovskite was prepared on a gram scale to investigate the influence of the chemical potential of the gas phase on the defect concentration, the oxidation states of the metals and the nature of the oxygen species at the surface. The oxide was treated at 450°C in nitrogen, synthetic air, oxygen, water vapor or CO and investigated for its properties as a catalyst in the oxidative dehydrogenation of propane both before and after treatment. After treatment in water vapor, but especially after treatment with CO, increased selectivity to propene was observed, but only when water vapor was added to the reaction gas. As shown by XRD, SEM, EDX and XRF, the bulk structure of the oxide remained stable under all conditions. In contrast, the surface underwent strong changes. This was shown by AP-XPS and AP-NEXAFS measurements in the presence of the different gas atmospheres at elevated temperatures. The treatment with CO caused a partial reduction of the metals at the surface, leading to changes in the charge of the cations, which was compensated by an increased concentration of oxygen defects. Based on the present experiments, the influence of defects and concentration of electrophilic oxygen species at the catalyst surface on the selectivity in propane oxidation is discussed.