Oxygen pyrochlore-type

The crystal structure of cadmium rhenium(V) oxide, as determined by single-crystal technique,1 is of the face-centered cubic pyrochlore type (a = 10.219 A.). The only positional parameter for the 48 (/) oxygens is x = 0.309 0.007 when rhenium is at the origin. The density, determined pycnometrically, is 8.82 0.03 g./cc., compared with the theoretical value of 8.83 g./cc. for Z = 8. The resistivity between 4.2 K and room temperature is very low (10-3-10-4 J2-cm.) and has a positive temperature coefficient. Over the same temperature range the magnetic susceptibility is low and temperature-independent. These properties indicate that cadmium rhenium(V) oxide exhibits metallic conductivity. 

There is a need to develop new types of oxide electrodes for reactions of technological importance with emphasis on both high electrocatalytic activity and stability. For example, pyrochlore-type oxides, e.g. lead or bismuth ruthenates, have shown excellent catalytic activity for the oxygen evolution and reduction reactions and should be further investigated to elucidate the reasons for such high activity. The long term stability of such ruthenate electrodes is questionable, however. 

Figure 9.4 Total conductivity of stabilized zirconia (a) and doped ceria (b) solid electrolytes [34—40], compared to the oxygen ionic conductivity of pyrochlore-type Cd2Zr2O7 5 [41], (Cd,Ca)2Ti2O7 5 [42], (Cd,Ca)2Sn2O7 s [43], and 241707 a [44].

The pyrochlore-type compounds, where the crystal structure is usually considered as a cation-ordered fluorite derivative with % vacant oxygen site per fluorite formula unit, constitute another large family of oxygen anion conductors [9, 33, 41—43, 84—88]. The unoccupied sites provide pathways for oxygen migration furthermore, the pyrochlore structure may tolerate formation of cation and anion vacancies, doping in both cation sublattices, and antistructural cation disorder. Regardless of these factors. 

Among other ion-conducting phases with fluorite-like structures, note should be taken of Y4Nl)Ox s, (Y,Nb,Zr)O2 8 solid solutions, and their derivatives (see Refs. [89-91] and references cited therein). The total conductivity of Y4NbO8.5-8 is essentially independent of the oxygen partial pressure, which may suggest a dominant ionic transport [90]. However, the conductivity level in this system is rather low, and similar to that in pyrochlore-type titanates and zirconates, although some improvements can be achieved by the addition of zirconia. 

Oxygen ion resistivity of polycrystalline material 18, 17.3.7 Pyrochlore-type structure 18, 17.3.7... 

Pyrochlore-type oxide 143 7.2.3. Operation of the A oxygen sensor 168... 

As for the four-electron oxygen reduction catalysts, (i) metal-based catalysts noble-metals (Pt, Ag, Au), noble-metal alloys, (ii) ceramic-based catalysts mono-metal oxides, mixed-metal oxides (spinel type, pyrochlore type, perovskite type), metal-sulfides, metal-carbides, metal-nitrides, (iii) organometallic catalysts metal-porphyrin, metal-phthalocyanine, have been reported. 

As the anion-exchange membrane fuel cell is the alkaline-based system, we can use non-platinum-based catalyst. This is a big advantage to lower the cost of fuel cells. Especially perovskite-type and pyrochlore-type oxides have high performance to oxygen-electrocatalysts which could be applicable to the cathode materials. Some oxides have also bifunctional activities as oxygen electrode catalyst to produce a reversible fuel cell thus, future deployment is expected. While, the big problems are stability of the base... 

Oxides with close-packed oxygen lattices and only partially filled tetrahedral and octahedral sites may also facilitate diffusion of metal ions in the unoccupied, interstitial positions. Finally, even large anions may diffuse interstitially if the anion sublattice contains structurally empty sites in lines or planes which may serve as pathways for interstitial defects. Examples are rare earth sesquioxides (e.g. Y2O3) and pyrochlore-type oxides (e.g. La2Zr207) with fluorite-derived structures and brownmillerite-type oxides (e.g. Ca2Fe205) with perovskite-derived structure. 

According to Ferreira-Aparicio et al. [190], the supply of surface oxygen species from the hydroxyls of the acidic supports can aid the formation of methoxo (CH ) species. Based on FTIR spectroscopy analysis of methane adsorption on alumina, Li et al. [191] observed the presence of two hydroxyl signals at 3750 and 3 665 cm which shifted to 3707 and 3640 cm upon adsorption of methane. Their results indicate the possibility of weak interaction between methane and surface hydroxyls, a phenomenon also observed with Ir catalysts during methane decomposition [192]. Similarly, on perovskite- and pyrochlore-type catalysts, the lattice oxygen species on the surface were found to assist the methane activatiOTi [167, 174, 193]. 

There is often a wide range of crystalline soHd solubiUty between end-member compositions. Additionally the ferroelectric and antiferroelectric Curie temperatures and consequent properties appear to mutate continuously with fractional cation substitution. Thus the perovskite system has a variety of extremely usehil properties. Other oxygen octahedra stmcture ferroelectrics such as lithium niobate [12031 -63-9] LiNbO, lithium tantalate [12031 -66-2] LiTaO, the tungsten bron2e stmctures, bismuth oxide layer stmctures, pyrochlore stmctures, and order—disorder-type ferroelectrics are well discussed elsewhere (4,12,22,23). 

The unit cell of pyrochlore can be considered as eight CaF2-type cells stacked as octants of a cube. There are two types of cells shown in Figure 6.21. They differ in the position of the oxygen vacancy and the relative positions of atoms A and B. Only two of the eight octants are shown to make it easier to visualize the relative positions of the three types of atoms. The octant on the lower left is type I and the other one is type II. There are four of each type, and they are not in adjacent cells. Atoms A and B are in ccp layers (a face-centered cubic structure) with oxygens in T layers. The type I cube has A ions located on face... 

As described in Section 8.2.6, along with YSZ, mixed oxygen-ion, and electron-conducting oxides with a perovskite-type structure, the so-called Aurivillius phase and pyrochlore materials are fundamentally used for the production of a variety of high-temperature electrochemical devices [50-58],... 

Oxygen (O2-) anion conductors - stabilized zir-conia, stabilized - bismuth oxide, - BIMEVOX, doped cerium dioxide, numerous perovskite-type - solid solutions derived from Ln(A)B (B") 03 (A = Ca, Sr, Ba B = Ga, Al, In B" = Mg, Ni, Co, Fe), La2Mo207 and its derivatives, pyrochlores based on Ln2Ti07. 

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