Defect spinel structure

In a number of studies a correlation was seen between the amount of nonstoi-chiometric oxygen in the spinel and the spinel s activity. It appears that excess oxygen consolidates the spinel s defect structure with a large number of active sites. Strong anodic polarization leads to ordering of this structure and thus to a decrease in catalytic activity. 

The sodium tungsten bronzes already described are examples of incomplete lattice defect structures. Iron(II) oxide is rather similar it has a rock-salt structure but is always deficient in iron. Some Fe ions are always present to maintain electrical neutrality. Fe304 has the spinel structure which has the same arrangement of ions as FeO. Fe203. has also the same arrangement and oxidation of FeO to FcgOg consists of the replacement of Fe2+ ions by two thirds of their number of Fe ions. 

Flexibility of the bulk/surface structure and reaction media effect. For such systems as manganese oxides, copper oxides, spinel iron oxides Fe304-y-Fe203 [4, 5, 24, 25 ], reaction media effect at enhanced temperatures (up to 400 °C ) and at prolonged (up to 10 h) exposures in reaction mixtures was found to remove all initial differences in the phase composition and defect structure. All extended defects were washed out due to interaction with a flux of point defects created by reaction media. As a result, a constant level of the catalytic activity was achieved for these oxide systems demonstrating apparent structural insensitivity of the reaction of CO oxidation. Hence, in this case, great flexibility of the oxide bulk structure allows to reach the same true steady state of the catalyst. 

The second modification of alumina is the less compact cubic y-Ai203 (d 3.4gcm ) it is formed by the low-temperature dehydration (<450°> of gibbsitc, y-Al(OH)3, or boehmite, y-AIO(OH). It has a defect spinel-type structure (p. 248) comprising a face-centred cubic (fee) arrangement of 32 oxide ions and a random occupation of 21 of the 24 available cation... 

Inverse and disordered spinels are called defect structures because all the identical crystallographic sites are not occupied by the same cation. A different defect structure is formed when spinels have disordered valencies. For example, the divalent cations in AB2 O4 may be replaced by equal numbers of and... 

The optimal material for magnetic recording media was, for many years, y-FejOs (maghemite). This form of FejOj, which has a defect-spinel crystal structure, can be prepared as small, elongated particles. The coercive field is produced within the required range by shape anisotropy (see Section 4.5.1). The process used to prepare small particles of... 

When or-Fe203 was used as the positive electrode in high-temperature lithium cells, the introduction of a small amount of lithium into the corundum-type structure caused the hexagonal-close-packed oxygen array to shear irreversibly to cubic-close packing which generated a defect /-Li FCjOj (spinel-type) structure. Further lithiation resulted in the formation of LiFe,Ojj thereafter, the reaction followed the same sequence as that shown in reactions (4), (5) and (6) [100]. The stability of the spinel structures at elevated temperatures, as well as the ability of the cubic close-packed oxygen array to accommodate lithium at the expense of... 

Solid electrolytes. These correspond to soHd materials in which the ionic mobility is insured by various intrinsic and extrinsic defects and are called solid ion conductors. Common examples are ion-conducting solids with rock salt or halite-type solids with a Bl structure (e.g., a-AgI), oxygen-conducting solids with a fluorite-type Cl structure (A"02), for instance CaF and yttria-stabilized zirconia (YSZ, ZrO with 8 mol.% Y O,), a pyro-chlore structure (A BjO ), perovskite-type oxides (A"B" 03), La Mo O, or solids with the spinel-type structure such as beta-aluminas (NaAl 0 ) for which the ionic conduction is ensured by Na mobility. 

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