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

Feng Wang; Delano P. Chong

doi:10.1071/CH23095

RESEARCH ARTICLE (Open Access)

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

Feng Wang

^A ^* and Delano P. Chong ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry and Biotechnology, School of Science, Computing and Engineering Technologies, Swinburne University of Technology, Hawthorn, Vic. 3122, Australia.

^B Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.

^* Correspondence to: fwang@swin.edu.au

Handling Editor: Amir Karton

Australian Journal of Chemistry 76(12) 854-863 https://doi.org/10.1071/CH23095

Submitted: 17 May 2023 Accepted: 1 September 2023 Published online: 27 September 2023

© 2023 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

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 5.31 ppm. Conversely, in AB and PB, two distinct sets of hydrogens emerge: protic hydrogens (H_p–N and H_p–P) and hydridic hydrogens (H_h–B). This leads to chemical shifts as small as 0.42 ppm in AB and as significant as 3.0 ppm in PB. The absolute isotropic NMR shielding constant (σ_B) of ¹¹B in DB is 85.40 ppm, in contrast to 126.21 ppm in AB and 151.46 ppm 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 193.93 eV 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.

Keywords: borane compounds, CEBE, core electron binding energy, DFT calculations, ¹H proton and ¹¹B NMR chemical shift–shielding constant, role of hydrogens and boron in boranes, valence ionisation energy spectrum.

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