Molecular aluminum hydrides identified by inelastic neutron scattering during H₂ regeneration of catalyst-doped NaAlH₂

Catalyst-doped sodium aluminum hydrides have been intensively studied as solid hydrogen carriers for onboard proton-exchange membrane (PEM) fuel cells. Although the importance of catalyst choice in enhancing kinetics for both hydrogen uptake and release of this hydride material has long been recognized, the nature of the active species and the mechanism of catalytic action are unclear. We have shown by inelastic neutron scattering (INS) spectroscopy that a volatile molecular aluminum hydride is formed during the early stage of H ₂ regeneration of a depleted, catalyst-doped sodium aluminum hydride. Computational modeling of the INS spectra suggested the formation of AlH ₃ and oligomers (AlH₃)_n (Al₂H ₆, Al₃H₉, and Al₄H₁₂ clusters), which are pertinent to the mechanism of hydrogen storage. This paper demonstrates, for the first time, the existence of these volatile species.