On the Origin of the Decay of the Photocatalytic Activity of TiO2 Powders Ground at High Energy

The influence of high-energy grinding on the photocatalytic activity of nanocrystalline titania (TiO 2 ) powders was investigated. Either in gas or in liquid reactions, the photocatalytic activity is observed to decrease with milling time. The structural and surface characterizations showed that the catalytic decrease is not correlated to the milling induced transformation of anatase TiO 2 into TiO 2 rutile via the high-temperature and high-pressure phase TiO 2 -II but to the introduction of defects and to the amorphization of the surface of the TiO 2 nanocrystals (nc). This has been correlated to the observed change of the photoluminescence properties of the powders. Spectrally resolved photoluminescence (PL) measurements as a function of temperature are sensitive to the well-established transformations of ground anatase TiO 2 nc into TiO 2 rutile via TiO 2 -II. For all TiO 2 nc in their different modifications, increasing the temperature produces a quenching of the PL intensity that is shown to follow a double activation energy law. These PL measurements first show that the electronic properties are strongly affected by the grinding process. Second, new states are generated in ground TiO 2, which have a higher PL quantum efficiency than those of the original TiO 2 nc. Thus, new channels of radiative recombination are opened due to defects produced by grinding, especially surface defects due to surface amorphization, and the number of electron−hole pairs, which are responsible for the photocatalytic activity, diminishes.