Regeneration of LiAlH4 at sub-ambient temperatures studied by multinuclear NMR spectroscopy

Lithium aluminium hydride (LiAlH 4 ) has long been identified as a viable hydrogen storage material, due to its high attainable theoretical gravimetric hydrogen capacity of 7.9 wt%. The main impediment to its viability for technical application is its limitation for regeneration. Recently, solvent-mediated regeneration has been achieved at room temperature using dimethyl-ether, Me 2 O, although the reaction pathway has not been determined. This in situ multinuclear NMR spectroscopy study ( 27 Al and 7 Li) has confirmed that the Me 2 O-mediated, direct synthesis of LiAlH 4 occurs by a one-step process in which LiAlH 4 ·xMe 2 O is formed, and does not involve Li 3 AlH 6 or any other intermediates. Hydrogenation has been shown to occur below ambient temperatures (at 0 °C) for the first time, and the importance of solvate adducts formed during the process is demonstrated