Vacancy accommodation

Even at lower concentrations (10 ), some interactions between point defects are possible. In forming new structures, the vacancies either order or they are eliminated. These vacancy accommodation processes are immensely important in heterogeneous oxidation catalysis using oxides and we examine these in the following sections. 

Figure 23. (a) linear string characteristic of Ce O, structure showing vacancies accommodated along the line. A cluster of primiiive cubic array of oxygen is also evidenced, showing six and seven... 

Finally we notice that in the p-type oxides CU2O and NiO, the presence of excess oxygen actually provides, through the formation of cation vacancies, a transport mechanism for the metal, while in an /i-type oxide like TiOi, the excess metal, by forming anion vacancies, provides a transport mechanism for oxygen. With /i-type oxides like ZnO and AljO, where the excess metal is accommodated interstitially, a transport mechanism is, of course, provided for the excess component itself. 

The oxygen vacancies then diffuse to the gas interface where they are annihilated by reaction with adsorbed oxygen. The important point, however, is that metal is consumed and oxide formed in the same reaction zone. The oxide drift has thus only to accommodate the net volume difference between the metal and its equivalent amount of oxide. In theory this net volume change could represent an increase or a decrease in the volume of the system, but in practice all metal oxides in which anionic diffusion predominates have a lower metal density than that of the original metal. There is thus a net expansion and the oxide drift is away from the metal. 

Several authors " have suggested that in some systems voids, far from acting as diffusion barriers, may actually assist transport by permitting a dissociation-recombination mechanism. The presence of elements which could give rise to carrier molecules, e.g. carbon or hydrogen , and thus to the behaviour illustrated in Fig. 1.87, would particularly favour this mechanism. The oxidant side of the pore functions as a sink for vacancies diffusing from the oxide/gas interface by a reaction which yields gas of sufficiently high chemical potential to oxidise the metal side of the pore. The vacancies created by this reaction then travel to the metal/oxide interface where they are accommodated by plastic flow, or they may form additional voids by the mechanisms already discussed. The reaction sequence at the various interfaces (Fig. 1.87b) for the oxidation of iron (prior to the formation of Fe Oj) would be... 

Tetrahedral and octahedral interstitial holes are formed by the vacancies left when anions pack in a ccp array, (a) Which hole can accommodate the larger ions (b) What is the size ratio of the largest metal cation that can occupy an octahedral hole to the largest that can occupy a tetrahedral hole while maintaining the close-packed nature of the anion lattice (c) If half the tetrahedral holes are occupied, what will be the empirical formula of the compound MVAV, where M represents the cations and A the anions ... 

Yakov Frenkel showed in 1926 that ideal crystals could not exist at temperatures above the absolute zero. Part of the ions leave their sites under the effect of thermaf vibrations and are accommodated in the interstitial space, leaving vacancies at the sites formerly taken up. Such point defects have been named Frenkel defects. These ideas were developed further by Walter Schottky in 1929, who pointed out that defects will also arise when individual ions or ion pairs are removed from the bulk... 

Internal boundaries are important in influencing the properties of single crystals in a number of ways. Impurities and other point defects, such as self-interstitials or vacancies, often congregate near to such interfaces. Moreover, because the regularity of the crystal structure is disrupted at the interface, unusual atom coordination can occur, allowing impurity atoms to be more readily accommodated. This in turn leads to differing, often enhanced, chemical reactivity, dissolution, and other physicochemical properties. 

Fig. 21. (a) The nature of the glide shear plane defects in three-dimensional projection and (b) in one layer of idealized structure, showing the novel glide shear process and the formation of glide shear plane defects. Filled circles are anion vacancies, (c) Schematic of glide shear. Glide defects accommodate the misfit at the interface between catalyst surface layers with anion vacancies (filled circles) and the underlying bulk (85,89). 

Transition metal oxides attract great interests mainly due to their redox nature, which is thought to be related with their flexible stmcture modiflcation under reductive and oxidative conditions. Such stmcture modiflcation takes place by forming so called crystallographic shear (CS) stmctures to accommodate anion vacancies in speciflc crystallographic planes by simultaneous shear displacement and crystal stmctural collapse [30-32]. High-resolution transmission electron microscopy (HRTEM) is a... 

Although this compound has the nominal formula FeO, stoichiometric material cannot exist as a stable phase at low pressures or at pressures in excess of 10 MPa. The non-stoichiometry is accommodated by oxidation of a proportion of the metal ions and the creation of cation vacancies (Lindsley, 1976). 

This behavior can be understood on the following basis. It was inferred from the comparison of the stability constants of the complexes that they reflect steric effects and that the vacancy in the 0-2 position is more prone to deformation than that in the a position [91, 92]. Then the abilities of these two kinds of sites to accommodate various metal cations being different and in favor of the U2 position, it is obvious that the reduction potentials should become less negative as the negative charge on the anion decreases. Furthermore, it has been proposed [30f 74] and experimental evidence [79] and... 

Dynamic ETEM experiments on CS defects have shown mat mey consume anion vacancies and grow (figure 3.7). These correlation studies indicate mat CS planes are secondary or detrimental to catalytic reactivity. They eliminate anion vacancies by accommodating the supersaturation of the vacancies in the reacting oxide catalyst and me catalyst reactivity (selectivity) begins to decrease with the onset of CS formation, i.e. CS planes are the consequence of catalyst reduction reactions rather than the origins of catalytic reactivity (Gai 1981,1992, 1993, Gai etfl/ 1982). 

Erom HRTEM studies, it is proposed that the majority of the bismuth molybdate phases can be derived from the fluorite structure, in which both the cation and anion vacancies can be accommodated within the fluorite framework (Buttrey et al 1987). Several industrial processes containing multicomponent bismuth molybdates may suffer loss of Mo oxides by volatilization under operating conditions, resulting in the loss of catalytic activity. Monitoring the catalyst microstructure using EM is therefore crucial to ensuring the continuity of these catalytic processes. 

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