Regeneration of ammonia borane from spent fuel materials

Summerscales, Owen T.; Gordon, John C.

doi:10.1039/c3dt50475a

Cited by 76 publications

(68 citation statements)

References 54 publications

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“…This is illustrated in Figure 6 where a mechanism of decomposition is suggested on the basis of both the present results and the results reported for LiN 2 H 3 BH 3 elsewhere [8]. A polymeric product of unknown composition forms, similar to the residues recovered upon the dehydrogenation of most of the B–N–H compounds [5,6,7,8,9,10,11,12,27]. The nature of such residues is unknown yet because of their difficult characterization (amorphous to X-ray and too complex composition for FTIR and NMR spectroscopy techniques).…”

Section: Discussion and Concluding Remarkssupporting

confidence: 76%

Lithium Hydrazinidoborane Ammoniate LiN2H3BH3·0.25NH3, a Derivative of Hydrazine Borane

et al. 2017

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Boron- and nitrogen-based materials have shown to be attractive for solid-state chemical hydrogen storage owing to gravimetric hydrogen densities higher than 10 wt% H. Herein, we report a new derivative of hydrazine borane N2H4BH3, namely lithium hydrazinidoborane ammoniate LiN2H3BH3·0.25NH3. It is easily obtained in ambient conditions by ball-milling N2H4BH3 and lithium amide LiNH2 taken in equimolar amounts. Both compounds react without loss of any H atoms. The molecular and crystallographic structures of our new compound have been confirmed by NMR/FTIR spectroscopy and powder X-ray diffraction. The complexation of the entity LiN2H3BH3 by some NH3 has been also established by thermogravimetric and calorimetric analyses. In our conditions, LiN2H3BH3·0.25NH3 has been shown to be able to release H2 at temperatures lower than the parent N2H4BH3 or the counterpart LiN2H3BH3. It also liberates non-negligible amounts of NH3 at temperatures lower than 100 °C. This is actually quite detrimental for chemical H storage, but alternatively LiN2H3BH3·0.25NH3 might be seen as a potential NH3 carrier.

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Section: Discussion and Concluding Remarkssupporting

confidence: 76%

Lithium Hydrazinidoborane Ammoniate LiN2H3BH3·0.25NH3, a Derivative of Hydrazine Borane

et al. 2017

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“…By weight, AB is rich in hydrogen (19.6 wt% H 2 ) and, coupled with low dehydrogenation temperatures and promising recycling routes, 1 it is clear to see why it has become a particularly attractive material for the study of mobile hydrogen-powered applications. However, the implementation of AB as a hydrogen storage material has been hindered by the presence of an incubation period prior to hydrogen release, foaming during hydrogen release, and the production of volatile by-products such as ammonia, diborane, and borazine, which poison the sensitive catalysts in hydrogen fuel cells.…”

Section: Introductionmentioning

confidence: 99%

Crystalline structure of an ammonia borane–polyethylene oxide cocrystal: a material investigated for its hydrogen storage potential

Ploszajski¹,

Billing²,

Cockcroft³

et al. 2018

CrystEngComm

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The crystalline structure of a cocrystal comprising ammonia borane (AB) and a short-chain polyethylene oxide (PEO or PEG) has been determined by single-crystal X-ray diffraction. The components interact via hydrogen bonds between each of the hydrogen atoms at the NH 3 end of the AB molecules and alternate oxygen atoms along the PEO backbone. The PEO chains in the structure exhibit an unusual conformation where their curvature reverses every 5 monomers, such that the polymer snakes through the crystal. This is the first time that an AB composite material has been determined to be a cocrystal, and no structure determination of a cocrystal to confine AB has been reported before.

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“…Many attempts have been made to efficiently regenerate AB waste. [13][14][15][16][17] A promising one-pot route involves treating the waste with hydrazine in liquid ammonia, which was shown to regenerate an AB waste surrogate successfully in 24 hours at 40 1C. 14 A further curiosity in terms of treating AB waste surrogates with liquid ammonia was demonstrated by Davis et al, who showed that some Lewis bases (specifically, pyridine and ammonia) were able to scavenge some of the residual high energy B-H bonds in the waste and rearrange them to form BH 3 .…”

mentioning

confidence: 99%

Dihydrogen vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

Ingram

Headen

Skipper

et al. 2018

Phys. Chem. Chem. Phys.

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The solvation structures of two systems rich in hydrogen and dihydrogen bonding interactions have been studied in detail experimentally through neutron diffraction with hydrogen/deuterium isotopic substitution. The results were analysed by an atomistic Monte Carlo simulation employing refinement to the experimental scattering data. The systems studied were the hydrogen storage material ammonia borane (NH 3 BH 3 , AB) dissolved in tetrahydrofuran (THF), and liquid ammonia (NH 3 ), the latter in which AB shows unusually high solubility (260 g AB per 100 g NH 3 ) and potential regeneration properties. The full orientational and positional manner in which AB-AB, AB-THF and AB-NH 3 pairs interact with each other were successfully deciphered from the wide Q-range total neutron scattering data. This provided an unprecedented level of detail into such highly (di)hydrogen bonding solute-solvent interactions. In particular this allowed insight into the way in which H-B acts as a hydrogen bond acceptor. The (di)hydrogen bonding was naturally determined to dictate the intermolecular interactions, at times negating the otherwise expected tendency for polar molecules to align themselves with anti-parallel dipole moments. Several causes for the extreme solubility of AB in ammonia were determined, including the ability of ammonia to (di)hydrogen bond to both ends of the AB molecule and the small size of the ammonia molecule relative to AB and THF. The AB B-H to ammonia H dihydrogen bond was found to dominate the intermolecular interactions, occurring almost three times more often than any other hydrogen or dihydrogen bond in the system. The favourability of this interaction was seen on the bulk scale by a large decrease in AB clustering in ammonia compared to in the dihydrogen bond-less THF.

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Regeneration of ammonia borane from spent fuel materials

Cited by 76 publications

References 54 publications

Lithium Hydrazinidoborane Ammoniate LiN2H3BH3·0.25NH3, a Derivative of Hydrazine Borane

Lithium Hydrazinidoborane Ammoniate LiN2H3BH3·0.25NH3, a Derivative of Hydrazine Borane

Crystalline structure of an ammonia borane–polyethylene oxide cocrystal: a material investigated for its hydrogen storage potential

Dihydrogen vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

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