Ga. Elshobaky et al., INVESTIGATION OF SOLID-SOLID INTERACTIONS BETWEEN PURE AND LI2O-DOPEDCOBALT AND FERRIC OXIDES, Thermochimica acta, 292(1-2), 1997, pp. 123-133
The solid-solid interactions between pure and lithium-doped cobalt and
ferric oxides have been investigated using TG, DTG, DTA and XRD techn
iques. The catalytic activity, in CO oxidation by O-2 at 400 degrees C
, was determined for each solid preheated in air at 700-1000 degrees C
. The amounts of lithium, expressed as mol% Li2O were 1.5 and 3. The r
esults obtained showed that Fe2O3 interacted readily with Co3O4 at tem
peratures starting from 700 degrees C to produce CoFe2O4 phase in well
crystallized form. The degree of propagation of this reaction increas
ed by increasing the heating temperature. However, a small portion of
unreacted free oxides was found in the case of pure-mixed solids heate
d at 1000 degrees C. Lithium oxide-doping stimulates the ferrite forma
tion to an extent proportional to its amount present. The stimulation
effect of lithium was evidenced by following up the change in the peak
heights of certain diffraction lines characteristic of Fe2O3, Co3O4 a
nd CoFe2O4 phases located at 'd' spacing of 2.69, 2.44 and 2.08 Angstr
om, respectively. The change of peak height of the diffraction line at
2.08 Angstrom as a function of firing temperature of pure- and doped-
mixed solids enabled the calculation of the activation energy of the f
errite formation (Delta E). The computed Delta E values were 57.3, 38.
4 and 28.8 kJ mol(-1) for pure-mixed solids specimen and those treated
with 1.5 and 3 mol% Li2O, respectively. The catalytic activity was fo
und to decrease by increasing the calcination temperature and also by
increasing the amount of Li2O due to the enhanced formation of CoFe2O4
phase which is less reactive than the free oxides, Co3O4 and Fe2O3. T
he promotion effect of lithium in the cobalt ferrite formation was att
ributed to an effective increase in the mobility of diffusion of react
ing cations. (C) 1997 Elsevier Science B.V.