DOE OSTI2011
Polycrystalline samples of (1-x) CeO{sub 2}-x/2 Bi{sub 2}O{sub 3} phases, where x is the atom fraction of bismuth have been synthesized by the precipitation process and after the thermal treatment at 600 {sup o}C, under air. Samples are first characterized by the X-ray diffraction and scanning electron microscopy. To determine the samples specific surface areas, Brunauer-Emmett-Teller (BET) analyses have been performed. In the composition range 0{<=}x{<=}0.20, a cubic solid solution with fluorite structure is obtained. For compositions x comprised between 0.30 and 0.90, two types of T' (or {beta}') and T (or {beta}) tetragonal phases, similar to the well-known {beta}' or {beta} Bi{sub 2}O{sub 3} metastable structural varieties, are observed. However, the crystal cell volumes of these {beta}' or {beta} Bi{sub 2}O{sub 3} phases increase with the composition x in bismuth: this might be due to the presence of defects or substitution by cerium atoms, in the tetragonal lattices. Using X-ray diffraction profile analyses, correlations between bismuth composition x and crystal sizes or lattice distortions have been established. The solid-gas interactions between these polycrystalline materials and air-CH{sub 4} and air-CO flows have been studied as a function of temperature and composition x, using Fourier transform infrared (FTIR) analyses of the conversions of CH{sub 4} and CO gases into the CO{sub 2} gas. The transformations of CH{sub 4} and CO molecules as a function of time and temperature are determined through the intensities of FTIR CO{sub 2} absorption bands. Using the specific surface areas determined from BET analyses, these FTIR intensities have been normalized and compared. For all bismuth compositions, a low catalytic reactivity is observed with air-CH{sub 4} gas flows, while, for the highest bismuth compositions, a high catalytic reactivity is observed with air-CO gas flows. -- Graphical abstract: Catalytic efficiencies of CeO{sub 2}-Bi{sub 2}O{sub 3}system: catalytic actions on methane (on the left) or carbon monoxide (on the right) of (1-x)CeO{sub 2}-x/2 Bi{sub 2}O{sub 3} samples, as a function of the fraction x, and for fixed temperatures: on the vertical axis, the intensities of CO{sub 2} FTIR absorption bands are reported. Strong efficiency of bismuth rich samples for CO conversion. Display Omitted Research highlights: {yields} Stabilization of metastable polymorph Bi{sub 2}O{sub 3} phases in the mix system [(1-x)CeO{sub 2}+(x/2)Bi{sub 2}O{sub 3}] at 600 {sup o}C. {yields} Solid gas interactions between this system and air-CO or air-CH{sub 4} gas flows at various temperatures and bismuth compositions. {yields} High efficiency of bismuth rich samples to convert CO into CO{sub 2}.