caa a22 4500 605510938 CHVBK 20210128100648.0 cr unu---uuuuu 210128e20150601xx s 000 0 eng 10.1007/s00894-015-2686-1 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2686-1 Quantum chemical investigation on the role of Li adsorbed on anatase (101) surface nano-materials on the storage of molecular hydrogen [Elektronische Daten] [V. Srinivasadesikan, P. Raghunath, M. Lin] Lithiation of TiO2 has been shown to enhance the storage of hydrogen up to 5.6wt% (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 × 7.655Å2 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 83kcal 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 27kcal 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 7.6kcal 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 0.32wt% under 100atm H2 pressure at 77K. The result of Bader charge analysis indicated that the reduction of Ti occurred depending on the Li atoms covered on the TiO2 surface. Springer-Verlag Berlin Heidelberg, 2015 Anatase nationallicence DFT+U nationallicence Hydrogen storage nationallicence Lithiation nationallicence TiO2(101) nationallicence VASP nationallicence Srinivasadesikan V. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut Raghunath P. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut Lin M. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-10 1610-2940 21:6<1 2015 21 894 https://doi.org/10.1007/s00894-015-2686-1 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2686-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Srinivasadesikan V. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut NATIONALLICENCE 700 1- Raghunath P. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut NATIONALLICENCE 700 1- Lin M. Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, 300, Hsinchu, Taiwan aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/6(2015-06-01), 1-10 1610-2940 21:6<1 2015 21 894