Molecular Design of a Reversible Hydrogen Storage Device Composed of the Graphene Nanoflake-Magnesium-H2 System.

Carbon materials such as graphene nanoflakes (GRs), carbon nanotubes, and fullerene can be widely used for hydrogen storage. In general, metal doping of these materials leads to an increase in their H2 storage density. In the present study, the binding energies of H2 to Mg species on GRs, GR-Mg m+ (m = 0-2), were calculated using density functional theory calculations. Mg has a wide range of atomic charges. In the case of GR-Mg (m = 0, Mg atom), the binding energy of one H2 molecule is close to 0, whereas those for m = 1 (Mg+) and 2 (Mg2+) are 0.23 and 13.2 kcal/mol (n = 1), respectively. These features suggest that GR-Mg2+ has a strong binding affinity toward H2, whereas GR-Mg+ has a weak binding energy. In addition, it was found that the first coordination shell is saturated by four H2 molecules, GR-Mg2+-(H2) n (n = 4). Next, direct ab initio molecular dynamics calculations were carried out for the electron-capture process of GR-Mg2+-(H2) n and a hole-capture process of GR-Mg+-(H2) n (n = 4). After electron capture, the H2 molecules left and dissociated from GR-Mg+: GR-Mg2+-(H2) n + e- → GR-Mg+ + (H2) n (H2 is released into the gas phase). In contrast, the H2 molecules were bound again to GR-Mg2+ after the hole capture of GR-Mg+: GR-Mg+ + (H2) n (gas phase) + hole → GR-Mg2+-(H2) n . On the basis of these calculations, a model device with reversible H2 adsorption-desorption properties was designed. These results strongly suggest that the GR-Mg system is capable of H2 adsorption-desorption reversible storage.

The structures and electronic states of zinc-water clusters Zn(n)(H2O)(m) (n = 1-32 and m = 1-3).

Ab initio and Density Functional Theory (DFT) calculations have been carried out for zinc-water clusters Zn(n)-(H2O)(m) (n = 1-32 and m = 1-3, where n and m are the numbers of zinc atoms and water molecules, respectively) to elucidate the structure and electronic states of the clusters and the interaction of zinc cluster with water molecules. The binding energies of H2O to zinc clusters were small at n = 2-3 (2.3-4.2 kcal mol(-1)), whereas the energy increased significantly in n = 4 (9.0 kcal mol(-1)). Also, the binding nature of H2O was changed at n = 4. The cluster size dependency of the binding energy of H2O accorded well with that of the natural population of electrons in the 4p orbital of the zinc atom. In the larger clusters (n > 20), it was found that the zinc atoms in surface regions of the zinc cluster have a positive charge, whereas those in the interior region have a negative charge with the large electron population in the 4p orbital. The interaction of H2O with the zinc clusters were discussed on the basis of the theoretical results.