Preparation by high-energy milling, characterization, and catalytic properties of nanocrystalline TiO2

Titanium dioxide (TiO2) is widely used for applications in heterogeneous photocatalysis. We prepared nanocrystalline powders of the anatase as well as the rutile modification by high-energy ball milling of the coarse grained source materials for up to 4 h. The resulting average grain size was about 20 nm. The morphology of the powders was investigated with transmission electron microscopy, X-ray powder diffraction, and BET surface area determination. Measurements of the catalytic activity reveal a maximum as a function of the milling time at about 40 min. This maximum could be explained by a superposition of two counteracting effects. The first one is the increase of the specific surface area resulting in an increase of the catalytic activity, and the second one is a change of the electronic structure at the surface of the TiO2 particles corresponding to a reduction of the surface. The latter one was confirmed by light absorption experiments, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy.