Electronic structure study of H3BXH3 (X═B, N and P) as hydrogen storage materials using calculated NMR and XPS spectra

Boron-based materials have been used for hydrogen storage applications owing to their high volumetric and gravimetric hydrogen density. The present study quantum mechanically investigates the electronic structures of three compounds: diborane (DB, B2H6), ammonia borane (AB, H3BNH3) and phosphine borane (PB, H3BPH3). The exploration is facilitated using calculated nuclear magnetic resonance (NMR) chemical shifts, together with outer valence ionisation potentials (IP) and core electron binding energy (CEBE). The findings show a distinct electronic structure for diborane, differing notably from AB and PB, which exhibit certain similarities. Noteworthy dissimilarities are observed in the chemical environments of the bridge hydrogens and terminal hydrogens in diborane, resulting in a substantial chemical shift difference of up to 5.31ppm. Conversely, in AB and PB, two distinct sets of hydrogens emerge: protic hydrogens (Hp–N and Hp–P) and hydridic hydrogens (Hh–B). This leads to chemical shifts as small as 0.42ppm in AB and as significant as 3.0ppm in PB. The absolute isotropic NMR shielding constant (σB) of 11B in DB is 85.40ppm, in contrast to 126.21ppm in AB and 151.46ppm in PB. This discrepancy indicates that boron in PB has the most robust chemical environment among the boranes. This assertion finds support in the calculated CEBE for B 1s of 196.53, 194.01 and 193.93eV for DB, AB and PB respectively. It is clear that boron in PB is the most reactive atom. Ultimately, understanding the chemical environment of the boranes is pivotal in the context of dehydrogenation processes for boron-based hydrogen storage materials.