Hydrogen Storage Applications of 1,2-Azaborines
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The development of safe and efficient hydrogen storage materials will aid in the transition away from fossil fuels toward a renewable, hydrogen-based energy infrastructure. Boron-nitrogen (BN) containing materials have attracted much attention due to their high hydrogen storage capacity and fast kinetics of hydrogen release. Furthermore, computational studies predict that hydrogen storage materials based on the BN-heterocycle 1,2-azaborine may enable reversible H2 uptake and release, with little additional energy input. This thesis develops the basic science needed for a hydrogen storage platform based on BN-heterocycles such as 1,2-azaborine. Chapter I is a review of recent developments in azaborine chemistry. Chapter II describes a regeneration scheme from a "spent" 1,2-azaborine hydrogen storage material to "fully charged" fuel using molecular H2 and H-/H+ equivalents. Chapter III describes the experimental determination of the resonance stabilization energy of 1,2-azaborines using reaction calorimetry. Chapter IV explores the effect of boron-substitution on the rate and extent of hydrogen release from BN materials. Chapter V describes work on a project unrelated to hydrogen storage, the synthesis and electronic parameter determination of the first 1,2- azaborine-containing phosphine ligand analog. This dissertation includes previously published and unpublished co-authored material.