Thermal stability and phase transformation of semi-crystalline mesostructured TiO2 in the presence of heteroelements

Abstract

The effect of the introduction of heteroelement (Si, P, Al, Ge, Ga and Zr) by direct synthesis on the thermal stability of mesostructured titania prepared by the soft templating pathway has been investigated. All materials have been surfactant-extracted with EtOH and calcined at different temperatures up to 900 °C. Ti4+ can be partially substituted by most of the investigated heteroelements but they mainly form an oxide amorphous phase surrounding the titania anatase particles. Results obtained by SAXS, X-Ray diffraction, Raman spectroscopy and manometry nitrogen adsorption-desorption show that the crystallization of the amorphous titania into nanosized anatase particles and the transition from anatase to rutile occur at higher temperature with the addition of the heteroelement. Even if the lattice distortion introduced by the partial Ti4+ substitution can participate to this phenomenon, it is mainly due the «glass » effect induced by the presence of the heteroelement in the TiO2 amorphous phase, which limits the growth of the nanosized anatase crystallites. However, when the crystallites reach a limit size, the collapse of the mesostructure occurs. With increasing the calcination temperature, the anatase titania particles become bigger and bigger, the transition from anatase to rutile takes place and the heteroelement can crystallize or be integrated in a crystalline phase. Among the considered heteroelements and by comparison with the bare mesostructured TiO2, the most beneficial effect is obtained in the presence of Si4+ and PO43− for which the mesostructure collapse at higher temperature by about two hundred Celsius degrees. Al3+ and Ge4+ enhance the thermal stability by about a hundred Celsius degrees and Ga3+ or Zr4+ have no significant effect on the temperature at which the mesostructure collapses.