Qu, Mengyang; Huang, Gang; Liu, Xinyi; Nie, Xuechuan; Qi, Chonghai; Wang, Huabin; Hu, Jun; Fang, Haiping; Gao, Yi; Liu, Wei-Tao; Francisco, Joseph S.; Wang, Chunlei

CHEMICAL SCIENCE

2022, 13, 2041-6520

Qu, Mengyang; Huang, Gang; Liu, Xinyi; Nie, Xuechuan; Qi, Chonghai; Wang, Huabin; Hu, Jun; Fang, Haiping; Gao, Yi; Liu, Wei-Tao; Francisco, Joseph S.; Wang, Chunlei

The lack of understanding of the molecular-scale water adsorbed on TiO2 surfaces under ambient conditions has become a major obstacle for solving the long-time scientific and applications issues, such as the photo-induced wetting phenomenon and designing novel advanced TiO2-based materials. Here, with the molecular dynamics simulation, we identified an ordered water bilayer structure with a two-dimensional hydrogen bonding network on a rutile TiO2(110) surface at ambient temperature, corroborated by vibrational sum-frequency generation spectroscopy. The reduced number of hydrogen bonds between the water bilayer and water droplet results in a notable water contact angle (25 +/- 5 degrees) of the pristine TiO2 surface. This surface hydrophobicity can be enhanced by the adsorption of the formate/acetate molecules, and diminishes with dissociated H2O molecules. Our new physical framework well explained the long-time controversy on the origin of the hydrophobicity/hydrophilicity of the TiO2 surface, thus help understanding the efficiency of TiO2 devices in producing electrical energy of solar cells and the photo-oxidation of organic pollutants.