Charge Trapping and Photoadsorption of O2 on Dehydroxylated TiO2 Nanocrystals—An Electron Paramagnetic Resonance Study

Abstract
The interaction of photogenerated charges with molecular oxygen was investigated on TiO2 nanocrystals by means of paramagnetic resonance (EPR) spectroscopy. Compared to photoactivation experiments in vacuum at P<106 mbar and T=140 K, the presence of O2 enhances the concentration of persistently trapped electron and hole centres—by a factor of ten—due to the formation of adsorbed O2 species. The photoadsorption of oxygen was also tracked quantitatively by pressure measurements, and the number of trapped charges, hole centres and O2 was found to correspond to ten electron–hole pairs per TiO2 nanocrystal. Conversely, in experiments at P<106 mbar with one trapped electron–hole pair per particle, charge separation is not persistent and completely reversible with respect to temperature. Heating to 298 K causes the total annihilation of photogenerated and trapped charges.