Lu-, Sm-, and Gd-Doped Ceria: A Comparative Approach to Their Structural Properties.
A room temperature structural study has been performed through the whole compositional range of the (Ce1-xLux)O2-x/2system by synchrotron X-ray diffraction and μ-Raman spectroscopy. Samples were synthesized by thermal treatment in air at 1373 K of coprecipitated mixed oxalates. A CeO2-based solid solution with a fluorite-type structure (F) was found to be stable up to x = 0.4, while at higher Lu content a (F + C) biphasic region was observed, with C being the cubic atomic arrangement typical of sesquioxides of the heaviest rare earths. A comparative approach including also results deriving from other (Ce1-xREx)O2-x/2systems (RE ≡ Gd and Sm) allowed us to conclude that the compositional extent of the F solid solution is a complex function of RE3+size and RE compressibility. On this basis, the dependence of ionic conductivity on the RE identity was interpreted as related both to the Ce4+/RE3+size closeness and to RE compressibility. Ce4+/RE3+dimensional issues were also revealed to rule the appearance of the hybrid structure observed in the two aforementioned systems, consisting of the intimate intergrowth of C microdomains within the F-based host lattice. Moreover, a more extended definition of F-based solid solution, including also the hybrid structure, is formulated; the latter is meant as a modification of the former, occurring when mainly RE-vacancy aggregates are incorporated into the host lattice in spite of isolated RE ions. By μ-Raman spectroscopy it was possible to demonstrate that the mechanism of oxygen vacancy formation is common to all the systems studied, provided that the structure of the F-based solid solution, also including the hybrid structure, is retained.
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.|CNR-ICMATE , Via De Marini 6, 16149 Genova, Italy.
Cristina
C
Artini
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.|CNR-SPIN Genova , Corso Perrone 24, 16152 Genova, Italy.
Marcella
M
Pani
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.|INSTM, Genova Research Unit , Via Dodecaneso 31, 16146 Genova, Italy.
Maria Maddalena
MM
Carnasciali
Elettra-Sincrotrone Trieste S.C.p.A. , ss 14, km 163.5, 34149 Basovizza, Trieste Italy.
Jasper Rikkert
JR
Plaisier
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.|CNR-SPIN Genova , Corso Perrone 24, 16152 Genova, Italy.
Giorgio Andrea
GA
Costa