First Principles Study of Hydrated/Hydroxylated TiO₂ Nanolayers: From Isolated Sheets to Stacks and Tubes

Periodic density functional calculations are carried out to investigate the structure and the stability of hydrated/hydroxylated TiO(2) layered compounds, nanosheets, and nanotubes. Due to a very efficient interlayer hydrogen bonding, the ABA-stacked "step 3" H(2)Ti(3)O(7) compound is found to be the most stable bulk phase, in agreement with the experiment. For single sheets in a water-rich environment other forms are instead favored, all close in energy, namely, "step 2" titanates, hydroxylized-anatase-like layers, and lepidocrocite-TiO(2). Finally, it is shown that a lepidocrocite-TiO(2) sheet, when hydroxylated only on one side, spontaneously forms a scroll-like nanotube. The nanotube diameter estimated from our models perfectly matches the approximately 3 nm value observed for the internal diameters of Na-free titania nanotubes.