Superwetting of TiO2 by light-induced water-layer growth via delocalized surface electrons.

Titania, which exhibits superwetting under light illumination, has been widely used as an ideal material for environmental solution such as self-cleaning, water-air purification, and antifogging. There have been various studies to understand such superhydrophilic conversion. The origin of superwetting has not been clarified in a unified mechanism yet, which requires direct experimental investigation of the dynamic processes of water-layer growth. We report in situ measurements of the growth rate and height of the photo-adsorbed water layers by tip-based dynamic force microscopy. For nanocrystalline anatase and rutile TiO2 we observe light-induced enhancement of the rate and height, which decrease after O2 annealing. The results lead us to confirm that the long-range attraction between water molecules and TiO2, which is mediated by delocalized electrons in the shallow traps associated with O2 vacancies, produces photo-adsorption of water on the surface. In addition, molecular dynamics simulations clearly show that such photo-adsorbed water is critical to the zero contact angle of a water droplet spreading on it. Therefore, we conclude that this "water wets water" mechanism acting on the photo-adsorbed water layers is responsible for the light-induced superwetting of TiO2. Similar mechanism may be applied for better understanding of the hydrophilic conversion of doped TiO2 or other photo-catalytic oxides.