On the structural stability of crystalline ceria phases in undoped and acceptor-doped ceria materials under in situ reduction conditions

Abstract

The reduction of pure and Sm-doped ceria in hydrogen has been studied by synchrotron-based in situ X-ray diffraction to eventually prove or disprove the presence of crystalline cerium hydride (CeH x ) phases and the succession of potential structural phase (trans)formations of reduced cerium oxide phases during heating-cooling cycles up to 1273 K. Despite a recent report on the existence of bulk and surface CeH x phases during reductive treatment of pure CeO 2 in H 2 , structural analysis by Rietveld refinement as well as additional 1 H-NMR spectroscopy did not reveal the presence of any crystalline CeH x phase. Rather, a sequence of phase transformations during the re-cooling process in H 2 has been observed. In both samples, the reduced/defective fluorite lattice undergoes at first a transformation into a bixbyite-type lattice with a formal stoichiometry Ce 0.583+ Ce 0.424+ O 1.71 and Sm 0.153+ Ce 0.393+ Ce 0.464+ O 1.73 , before a transformation into rhombohedral Ce 7 O 12 takes place in pure CeO 2 . This phase is clearly absent for the Sm-doped material. Finally, a triclinic Ce 11 O 20 phase appears for both materials, which can be recovered to room temperature, and on which a phase mixture of bixbyite Ce 0.663+ Ce 0.344+ O 1.67 , rh-Ce 0.603+ Ce 0.404+ O 1.70 and tri-Ce 0.483+ Ce 0.524+ O 1.76 (for pure CeO 2 ) or bixbyite Sm 0.153+ Ce 0.473+ Ce 0.384+ O 1.69 and tri-Sm 0.153+ Ce 0.313+ Ce 0.544+ O 1.77 (for Sm-doped CeO 2 ) prevails. The absence of the rhombohedral phase indicates that Sm doping leads to the stabilization of the bixbyite phase over the rhombohedral one at this particular oxygen vacancy concentration. It is worth noting that recent work proves that hydrogen is indeed incorporated within the structures during the heat treatments, but under the chosen experimental conditions it has apparently no effect on the salient structural principles during reduction.