Kinetics of the amorphous—anatase phase transformation in copper doped titanium oxide

Samples of TiO2 doped with 2 and 5 mol% of Cu2+ were prepared by the sol-gel process. Titanium(IV) isopropoxide and copper(II) nitrate were used as precursors. The samples were prepared as monolithic shapes, dried at 80°C for 72 h and heat treated at various temperatures in the range 200–900°C for 2 h. The structural transformation and texture of the samples were investigated by X-ray powder diffraction (XRD) and nitrogen adsorption. Significant changes were observed during the crystallization process; on the one hand, the crystallization profiles show that crystallization occurs uniformly and is practically insensitive to the dopant concentration, but when the transformation at a given temperature is followed as a function of time, the rate of the amorphous-anatase transformation is larger for the sample containing 2 mol% Cu2+. Electron spin resonance (ESR) results show that in this sample there is no segregation of Cu2+ ions. The sample containing 2 mol% of Cu2+ was selected for the kinetic studies and the temperatures selected were 300, 325, 350, 375 and 400°C, which were taken from the amorphous to anatase crystallization profile. An activation energy of 137 ± 4 kJ/mol for the crystallization process was estimated from the kinetic data. These results showed that the effect of the open structure present in the TiO2 amorphous phase provides the atomic mobility required for the crystallization. On the other hand, the differences in the crystallization rate due to the amount of Cu2+ were explained by the segregation of copper ions to the surface of the samples.