Vacancy activity

M. Migschitz and W Pfeiler, Vacancy activation enthalpies of Au-Fe alloys determined from SRO-induced resistivity changes, A/a/. Sci. Eng. A206 I55 (1996)... 

Fig. 20. (a) Active sites observed by in situ atomic-resolution ETEM structural modification of VPO in n-butane along (201) indicates the presence of in-plane anion vacancies (active sites in the butane oxidation) between vanadyl octahedra and phosphate tetrahedra. (b) Projection of (010) VPO (top) and generation of anion vacancies along (201) in n-butane. V and P are denoted. Bottom model of novel glide shear mechanism for butane oxidation catalysis the atom arrowed (e.g., front layer) moves to the vacant site leading to the structure shown at the bottom. 

As has been discussed above, knowledge of the dispersion of the catalyst is extremely difficult to obtain, especially in the promoted systems. This is the main obstacle to clear differentiation between the promoter models proposed and remains so today. Chemisorption techniques to count the active sites present on the sulfided surfaces have had limited success. 02 chemisorption has been associated with edge vacancies (active sites) on pure M0S2 (100). However, the same authors showed that it was impossible to correlate activity and amount of 02 chemisorbed on Co- or Ni-promoted molybdenum sulfide (101). The use of other test molecules was disputable, particularly NO, which can strongly modify the structure of the surface during the measurement (102). 

Assuming that the concentration of oxygen ions is essentially constant along the membrane (or expressing the vacancy activity as the ratio of vacancy and anion concentrations), it is possible to write ... 

First-principles calculations were done to examine the effect of oxygen vacancies in Li2Mn03 on lithium extraction from the crystal. As the ratio of O vacancies increases, the redox potential associated with the lithium extraction decreases, and the Mn contribution in the charge compensation for the lithium extraction increases. These findings indicate that the introduction of O vacancies activates the Mn sites as the redox center in the lithium extraction process. However, the lithium extraction from Li2Mn03 tends to cause successive O2 evolution from the crystal. This results in a high O vacancy... 

Sodium Vacancy Activation Barriers in the Na4pe3(P04)2(P207) Structure... 

Estimations show that at T 1000 K and vacancy activation energy 1 eV, the relative vacancy concentration is (n/AO = 10. Note that the relative vacancy con-... 

The vacancy is very mobile in many semiconductors. In Si, its activation energy for diffusion ranges from 0.18 to 0.45 eV depending on its charge state, that is, on the position of the Fenni level. Wlrile the equilibrium concentration of vacancies is rather low, many processing steps inject vacancies into the bulk ion implantation, electron irradiation, etching, the deposition of some thin films on the surface, such as Al contacts or nitride layers etc. Such non-equilibrium situations can greatly affect the mobility of impurities as vacancies flood the sample and trap interstitials. 

Haeany Solution Model The initial model (37) considered the adsorbed phase to be a mixture of adsorbed molecules and vacancies (a vacancy solution) and assumed that nonideaUties of the solution can be described by the two-parameter Wilson activity coefficient equation. Subsequendy, it was found that the use of the three-parameter Flory-Huggins activity coefficient equation provided improved prediction of binary isotherms (38). 

For an ion to move through the lattice, there must be an empty equivalent vacancy or interstitial site available, and it must possess sufficient energy to overcome the potential barrier between the two sites. Ionic conductivity, or the transport of charge by mobile ions, is a diffusion and activated process. From Fick s Law, J = —D dn/dx), for diffusion of a species in a concentration gradient, the diffusion coefficient D is given by... 

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

Typical values of the energy to form vacancies are for silver, lOSkJmol and for aluminium, 65.5kJmol These values should be compared with the values for the activation enthalpy for diffusion which are given in Table 6.2. It can also be seen from the Table 6.2 that die activation enthalpy for selfdiffusion which is related to the energy to break metal-metal bonds and form a vacant site is related semi-quantitatively to the energy of sublimation of the metal, in which process all of the metal atom bonds are broken. 

The value of the activation energy approaches 50000 near the stoichiometric composition. This diffusion process therefore approximates to the selfdiffusion of metals at stoichiometty where the vacancy concentration on the carbon sub-lattice is small. 

The diffusion coefficient corresponding to the measured values of /ch (D = kn/4nRn, is the reaction diameter, supposed to be equal to 2 A) equals 2.7 x 10 cm s at 4.2K and 1.9K. The self-diffusion in H2 crystals at 11-14 K is thermally activated with = 0.4 kcal/mol [Weinhaus and Meyer 1972]. At T < 11 K self-diffusion in the H2 crystal involves tunneling of a molecule from the lattice node to the vacancy, formation of the latter requiring 0.22 kcal/mol [Silvera 1980], so that the Arrhenius behavior is preserved. Were the mechanism of diffusion of the H atom the same, the diffusion coefficient at 1.9 K would be ten orders smaller than that at 4.2 K, while the measured values coincide. The diffusion coefficient of the D atoms in the D2 crystal is also the same for 1.9 and 4.2 K. It is 4 orders of magnitude smaller (3 x 10 cm /s) than the diffusion coefficient for H in H2 [Lee et al. 1987]. 

The complex coordination chemistry of Pb" is also beginning to be actively explored and some unusual stereochemistries are emerging. Thus, the mononuclear ( ) -nitrato)bis(phenanthrolene)(A-thiocyanato) complex [Pb(phen)2(NCS)( ) -NO3)] has 7-coordinate Pb" with a large vacancy... 

For small enough temperature steps (< lOK) during small step annealing the vacancy concentration practically remains constant and corresponds to the instantaneous aimealing temperature. This allows for an easy analysis of SRO-kinetics yielding SRO-relaxation times and SRO-activation enthalpies, which by usual interpretation correspond to H +Hf. 

---