The emphasis of this research is to study and elucidate the underlying mechanisms of reversible hydrogen storage in pristine and Ti-doped sodium aluminum hydrides using molecular modeling techniques. An early breakthrough in using complex metal hydrides as hydrogen storage materials is from the research on sodium alanates by Bogdanovic et al., in 1997 reporting reversible hydrogen storage is possible at moderate temperatures and pressures in transition metal doped sodium alanates. Anton reported titanium salts as the best catalysts compared to all other transition metal salts from his further research on transition metal doped sodium alanates. However, a few questions remained unanswered regarding the role of Ti in reversible hydrogen storage of sodium alanates with improved thermodynamics and kinetics of hydrogen desorption.;The first question is about the position of transition metal dopants in the sodium aluminum hydride lattice. The position is investigated by identifying the possible sites for titanium dopants in NaAlH4 lattice and studying the structure and dynamics of possible compounds resulting from titanium doping in sodium alanates. The second question is the role of titanium dopants in improved thermodynamics of hydrogen desorption in Ti-doped NaAlH4. Though it is accepted in the literature that formation of TiAl alloys (Ti-Al and TiAl3) is favorable, reaction pathways are not clearly established. Furthermore, the source of aluminum for Ti-Al alloy formation is not clearly understood. The third question in this area is the role of titanium dopants in improved kinetics of hydrogen absorption and desorption in Ti-doped sodium alanates. This study is directed towards addressing the three longstanding questions in this area. Thermodynamic and kinetic pathways for hydrogen desorption in pristine NaAlH4 and formation of Ti-Al alloys in Ti-doped NaAlH 4, are elucidated to understand the underlying mechanisms of hydrogen desorption.;Density functional theory formalism as implemented in CASTEP (Cambridge Serial Total Energy Package) is used to study the structure and energetics of pristine and Ti-doped sodium alanates. From investigations of various models of sodium alanates with Ti dopants, it is shown that the difference between the energy required for Ti→SNa (Ti-substituted Na at the lattice site on the surface) and Ti→TI (Ti placed on top of the surface interstitial SI site) is 0.003 eV atom-1, and is minimal compared to other models. Since less energy is required for Ti→S Na and Ti→TI, these two sites (SNa and T I) would be preferred by the Ti dopants. In Ti→SNa model, Ti is coordinated to two aluminum and seven hydrogen atoms resulting in the possible formation of a TiAl2H7 complex. At elevated temperatures (423 and 448 K), the number of aluminum atoms coordinating with titanium in the complex increase from two (at distances in the 2.6-2.7 A range) to five (at distances in the 2.6-2.7 A range). Besides the formation of a Ti-Al-H complex, Al-Al association (with a 2.97 A bond length) is also seen from the DFT-MD results. In the case of Ti→TI, Ti is coordinated to two aluminum and two hydrogen atoms resulting in the possible formation of a TiAl2H2 complex. TiAl2 H2 complex becomes TiAl3H6 and TiAl 3H7 at elevated temperatures of 423 and 448 K, respectively.;The investigation of thermodynamics pathways in Ti-doped sodium alanates illustrates a three step reaction pathway to the formation of TiAl3 (Ti and AlH3 after the first reaction, TiAl after the second and finally TiAl3). This investigation also suggests aluminum in its +3 oxidation state present in aluminum hydride species is responsible in the formation of Ti-Al alloys. From kinetics studies, the proposed mechanism is related to transition from AlH4- to AlH6 3-. The rate limiting step is determined to be associated with hydrogen evolution from association of AlH3 species nucleating aluminum phase. This step is 15 kJ/mol higher than the nearest highest barrier in the reaction path related to transition from AlH52- to AlH63-. From the DFT-MD simulations, it is observed that the titanium dopants are present on the surface during the entire simulation time and exhibit the role in catalytic splitting of hydrogen from surrounding AlH4 groups. Besides the catalytic role, Ti dopants also form bonds with Al, and we also see that the AlH4 groups on the surface and that are present in the sub-surface layers are drawn towards the Ti dopants. This association of Al around titanium indicates the initiation of Al nucleation site facilitated by Ti dopants residing on the surface.
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