An XPS and reduction study of PrCoO3

The perovskite-type oxide PrCoO3 has been studied by means of X-ray photoelectron spectroscopy (XPS), reduction in H2 and X-ray diffraction. Two types of oxygen were detected: lattice oxygen (binding energy = 528.4 eV) and adsorbed oxygen (binding energy = 530.9 eV). The increase in relative intensity of the peak corresponding to the latter species after reduction of PrCo03 to 3e− per molecule is assigned to the formation of hydroxyl groups. Temperature-programmed reduction (TPR) results showed two reduction steps: to 1 e− per molecule (Co3.1 → Co2+) at 475 to 635 K, and to 3e− per molecule (Co21 → Co0) at 725 to 815 K. Reduction in the first and second steps occurs according to the contracting sphere model and the nucleation mechanism, respectively. Reduction of Co3+ to Co2+ causes minimal structural changes in the perovskite. Reduction to 3e− per molecule yielded Pr2O3 and metallic cobalt. After this reduction and reoxidation at 973 K, the perovskite structure was regained. By XPS and TPR it was shown that PrCo03 is more easily reducible than LaCo03. It is concluded that the cation in the A position of the structure plays a significant role in the bulk and surface properties of LnCo03 (Ln, lanthanide elements) oxides.