Fluorites mixed oxides

BaAn" 03 (An = Th Am) all have the perovskite strueture and are obtained from the aetinide dioxide. In aeeord with normal redox behaviour, the Pa and U eompounds are only obtainable if O2 is rigorously exeluded, and the Am eompound if O2 is present. Aetinide dioxides also yield an extensive series of nonstoiehiometrie, mixed oxide phases in whieh a seeond oxide is ineorporated into the fluorite lattiee of the An02. The UO2/PUO2 system, for example, is of great importanee in the fuel of fast-breeder reaetors. 

Ceria is another type of mixed conducting oxide which has been shown already to induce electrochemical promotion.71 Ceria is a catalyst support of increasing technological importance.73 Due to its nonstoichiometry and significant oxygen storage capacity it is also often used as a promoting additive on other supports (e.g. y-A Cb) in automobile exhaust catalysts.79 It is a fluorite type oxide with predominant n-type semiconductivity. The contribution of its ionic conductivity has been estimated to be 1-3% at 350°C.71... 

It was rather surprising when Hund and Durrwachter [312] found that La20s is miscible with TI1O2 to a great extent (52 mole per cent) whilst still preserving the cubic fluorite structure. The lattice constant of the mixed oxide has an a value 5.645 A compared to 5.592 A for TI1O2. The lattice constants of some orthorhombic perovskite and cubic garnet-type europium compounds are listed in Table 22. 

For the last twenty years, the research effort on ceria-based catalytic materials has steeply increased (I). An important part of this effort has been devoted to M/Ce02 and closely related systems, i.e. catalysts consisting of transition metals supported on the higher rare earth oxides (Ce02, Pi02-x Tb02-it), and ceria-containing mixed oxides, all of them with fluorite-related structure. 

The topic of mixed conduction in nonstoichiometric oxides was reviewed by Tuller [24], and his comprehensive paper is recommended to the reader interested in more detail concerning the role of multivalent dopants on the defect chemistry of fluorite and fluorite-related oxides, and corresponding transport properties. Equations which express the oxygen flux in solid solutions of, e.g.. 

Praseodymium is one of the possible "new" additives, which today attracts more and more attention. In fact, it was demonstrated that the oxygen exchange occurs at lower temperature on cerium-praseodymium mixed oxides than on ceria [7]. Furthermore, high temperature pretreatment does not affect the oxygen exchange capacity (OSC) of the mixed oxides. Moreover, high surface area PrOy-Zr02 materials with a fluorite-type structure were also prepared by the sol-gel way [7, 8]. 

We prepared by sol-gel some thermally stable Zro.io(Cei-xPrx)o.9o02 mixed oxides (x between 0 and 0.75) with a fluorite-type structure. This structure was confirmed by the presence, in the Raman spectrum, of a single band ca. 460 cm characteristic of the M-0 vibration in the fluorite-type structure. Moreover, the band position and the shoulder at 570 cm indicate the presence of oxygen vacancies probably associated with praseodymium cations. Consequently, high OSCs appears to be the result of the presence of both cerium and praseodymium atoms. Thus, addition of praseodymium atoms into zirconia-ceria oxides appears to be very promising for the design of new automotive catalysts. 

OPCM route of ceria—zirconia solid solutions synthesis appears to be reasonably flexible approach allowing to make rather broad substitution in cation and anion sublattices of fluorite-like oxides without appearance of new phases provided homogeneous mixing of starting salts is ensured. Reasonably high dispersion of samples thus obtained and disordered bulk and surface structure makes them promising candidates as catalysts and supports for red-ox reactions. 

Mixed Ce/REO s (e.g., La, Y, Hf) and Ce/Zr mixed oxides are often more easily reduced than Ce02 itself. These ions are either similar in size to Ce or smaller, providing for increased oxygen mobility. However, the (defective) fluorite structure is retained during the reduction unless the doping exceeds several %.i38,i4o,i5o p j. degree of reduction vs. temperature, some of the differences in the literature are undoubtedly due to differences in the intimacy of mixing between the oxides. 

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