Phase Behavior and Crystal Structure of Perovskite-Type Rare Earth Complex Oxides

Several compounds of rare earth complex oxides containing manganese and titanium were synthesized in Ar, and their crystal structures were analyzed by powder X-ray diffraction data and Rietveld method. Structures of A0.67Ln0.33 Mn0.33Ti0.6703（A = Ca or Sr and Ln = rare earth） were found to have orthorhombic symmetry with the space group Pnrna, and their interatomic distances and bond angles were obtained. This space group was also derived from electron microscopic study. Electrical conductivity of Cao.67Ln0.33Mn0.33Ti0.6703 for several rare earth elements showed a semiconducting property with the activation energy of 0.4 eV. Some of these compounds of the strontium system show the antiferromagnetic properties below 10 K.

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.

Phase Behavior of BaLn_2Mn_2O_7 (Ln=Rare Earth) with a Layered Perovskite Structure

Many phases appear in BaLn 2Mn 2O 7 family (Ln=rare earth) belonging to one of the Ruddlesden-Popper type compounds, depending upon the experimental conditions such as heating conditions when prepared and composition. Some of these phases were characterized by powder X-ray diffraction method using Rietveld analysis. These phases have only a little difference in crystal structure which has fundamentally K 2NiF 4 type structure, although the X-ray diffraction patterns are clearly different: a little deformation or tilting of the oxygen octahedron surrounding a central manganese ion composing the main frame of this structure induce these different diffraction patterns. Phase behavior of these compounds, mainly the detailed relation between various phases in BaTb 2Mn 2O 7, was refined including the data of high temperature X-ray diffractometry.

Active manganese oxide on MnOx-CeO2 catalysts for low-temperature NO oxidation：Characterization and kinetics study

MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency（TOF） was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.