Quantum chemical investigation on the role of Li adsorbed on anatase (101) surface nano-materials on the storage of molecular hydrogen

Lithiation of TiO₂ has been shown to enhance the storage of hydrogen up to 5.6 wt% (Hu et al. J Am Chem Soc 128:11740–11741, 2006). The mechanism for the process is still unknown. In this work we have carried out a study on the adsorption and diffusion of Li atoms on the surface and migration into subsurface layers of anatase (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT+U). The model consists of 24 [TiO₂] units with 11.097 × 7.655 Å² surface area. Adsorption energies have been calculated for different Li atoms (1–14) on the surface. A maximum of 13 Li atoms can be accommodated on the surface at two bridged O, Ti-O, and Ti atom adsorption sites, with 83 kcal mol⁻¹ adsorption energy for a single Li atom adsorbed between two bridged O atoms from where it can migrate into the subsurface layer with 27 kcal mol⁻¹ energy barrier. The predicted adsorption energies for H₂ on the lithiated TiO₂ (101) surface with 1–10 Li atoms revealed that the highest adsorption energies occurred on 1-Li, 5-Li, and 9-Li surfaces with 3.5, 4.4, and 7.6 kcal mol⁻¹, respectively. The values decrease rapidly with additional H₂ co-adsorbed on the lithiated surfaces; the maximum H₂ adsorption on the 9Li-TiO₂(a) surface was estimated to be only 0.32 wt% under 100 atm H₂ pressure at 77 K. The result of Bader charge analysis indicated that the reduction of Ti occurred depending on the Li atoms covered on the TiO₂ surface.