Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature

doi:10.1016/j.ijhydene.2010.12.129

International Journal of Hydrogen Energy

Volume 36, Issue 8, April 2011, Pages 4958-4966

https://doi.org/10.1016/j.ijhydene.2010.12.129 Get rights and content

Abstract

There has been rapidly growing interest for materials suitable to store hydrogen in solid state for transportation of hydrogen that requires materials with high volumetric and gravimetric storage capacity. B-N compounds such as ammonia-triborane, ammonia-borane and amine-borane adducts are well suited for this purpose due to their light weight, high gravimetric hydrogen storage capacity and inclination for bearing protic (N-H) and hydridic (B-H) hydrogens. In addition to them, more recent study [26] has showed that hydrazine borane with a gravimetric hydrogen storage capacity of 15.4% wt needs to be considered as another B-N compound that can be used for the storage of hydrogen. Herein we report for the first time, metal catalyzed hydrolysis of hydrazine borane (N₂H₄BH₃, HB) under air at room temperature. Among the catalyst systems tested, rhodium(III) chloride was found to provide the highest catalytic activity in this reaction. In the presence of rhodium(III) chloride, the aqueous solution of hydrazine borane undergoes fast hydrolysis to release nearly 3.0 equivalent of H₂ at room temperature with previously unprecedented H₂ generation rate TOF = 12000 h^�?�1. More importantly, it was found that in the catalytic hydrolysis of hydrazine borane the reaction between hydrazine borane and water proceeds almost in stoichiometric proportion indicating that the efficient hydrogen generation can be achieved even from the highly concentrated solution of hydrazine borane or in the solid state when water added to the solid hydrazine borane. This finding is crucial especially for on-board application of the existing system. The work reported here also includes (i) finding the solubility of hydrazine borane plus its stability against self-hydrolysis in water, (ii) the definition of reaction stoichiometry and the identification of reaction products for the catalytic hydrolysis of hydrazine borane, (iii) the collection of wealthy kinetic data to demonstrate the effect of substrate and catalyst concentrations on the hydrogen generation rate and to determine the rate law for the catalytic hydrolysis of hydrazine borane, (iv) the investigation of the effect of temperature on the rate of hydrogen generation and determination of activation parameters (E_a, ΔH^#, and ΔS^#) for the catalytic hydrolysis of hydrazine borane.

Introduction

There has been rapidly growing interest for suitable hydrogen storage materials because the efficient storage of hydrogen is still one of the key issues of �?Hydrogen Economy” [1], [2], [3]. At this concern, various solid materials, such as metal nitrides and imides [4], carbon nanotubes [5], TiO₂ nanotubes [6], zeolites [7], organic-polymers [8], metal-organic frameworks [9] and CBN compounds [10] have been considered for hydrogen storage. Among these materials boron based compounds seem to be the most attractive hydrogen storage materials as they have low formula weight and high hydrogen density [11]. Especially, sodium borohydride (NaBH₄) [12], [13], ammonia-borane (H₃NBH₃) [14], [15], [16], [17], [18], [19], [20], [21], dimethylamine-borane ((CH₃)₂HNBH₃) [22], and ammonia-triborane (H₃NB₃H₇) [23] have been tested as chemical hydrogen storage materials which can easily release hydrogen gas upon hydrolysis under mild conditions (at room temperature under air).

Herein we report, for the first time, the hydrogen generation from the catalytic hydrolysis of another boron based compound, hydrazine borane (N₂H₄BH₃, HB) [24] which appears to be a promising hydrogen storage material. Hydrazine borane has a gravimetric hydrogen storage capacity of 15.4% wt which is greater than the 2015 target of U.S. Department of Energy (9% wt hydrogen for a material to be practically applicable) [25]. Although hydrazine borane has been shown to give off very slowly its hydrogen up to 6.5% wt upon heating to 150 °C in 16 h [26], here we demonstrate that efficient hydrogen release can be achieved by its metal catalyzed hydrolysis (Eq. (1)) at room temperature (vide infra). $N_{2} H_{4} {BH}_{3} (s) + 2 H_{2} O (I) \to_{RT}^{catalyst} N_{2} H_{5}^{+} (aq) + {BO}_{2}^{�?�} (aq) + 3 H_{2} (g)$

Among the catalyst systems tested in this reaction, rhodium(III) chloride was found to provide the highest catalytic activity. In the presence of rhodium(III) chloride, complete hydrolysis of hydrazine borane can be achieved not only in aqueous solution, but also in the solid state when water is added dropwise to the solid hydrazine borane.

Section snippets

Materials

Ruthenium(III) chloride (RuCl₃), rhodium(III) chloride (RhCl₃.xH₂O), Rh/Al₂O₃, Ru/Al₂O₃, NaBH₄, tetrahydrofuran (99.9%) and Sodium Zeolite-Y (Si/Al = 2.5) were purchased from Aldrich. Hydrazine hydrate (N₂H₄.H₂O) and hydrazine sulfate ((N₂H₆)SO₄) were purchased from Merck. THF was distilled over sodium/benzophenone under argon and stored in the drybox (H₂O and O₂ < 1 ppm). Rhodium(III) chloride was recrystallized from water and the water content of RhCl₃·xH₂O was determined by TGA and found to

Synthesis, characterization, properties and catalytic hydrolysis of hydrazine borane

Hydrazine borane (N₂H₄BH₃) was prepared according to procedure described elsewhere [30], which involves the reaction of dihydrazine sulfate with sodium borohydride in THF at room temperature (Eq. (2)). The purity of the as-prepared hydrazine borane was checked by melting point determination, ATR-IR, DP-MS, ¹H and ¹¹B NMR spectroscopic methods and their results (vide supra) are in agreement with the previously reported literature data [30]. ${(N_{2} H_{5})}_{2} {SO}_{4} + {NaBH}_{4} \underset{THF, RT}{\to} 2 N_{2} H_{4} {BH}_{3} + {Na}_{2} {SO}_{4} + 2 H_{2}$

Before

Conclusion

In summary, we demonstrated for the first time that a rapid hydrogen generation can readily be achieved from the hydrolysis of hydrazine borane by using RhCl₃ precatalyst, in which bulk Rh(0) found to be active catalyst providing apparent TOF values of 12000 h^�?�1 even at room temperature. The hydrolysis of hydrazine borane is stoichiometric and goes to completion. Hydrogen can be generated even by dropwise adding of liquid water to the solid hydrazine borane. This catalytic system possesses high

Acknowledgements

Partial support by Turkish Academy of Sciences and TUBITAK (2218-Research Fellowship) is gratefully acknowledged.

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¹: On the leave absence from Department of Chemistry, Dokuz Eylül University, 35160 Izmir, Turkey.

²: Present address: Department of Chemistry, Yüzüncü Yil University, 65080 Van, Turkey.

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Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature

Abstract

Introduction

Section snippets

Materials

Synthesis, characterization, properties and catalytic hydrolysis of hydrazine borane

Conclusion

Acknowledgements

Int J Hydrogen Energ

Int J Hydrogen Energ

Int J Hydrogen Energ

J Alloys Compd

Int J Hydrogen Energ

Int J Hydrogen Energ

Int J Hydrogen Energ

Int J Hydrogen Energ

Appl Catal B

Int J Hydrogen Energ

J Power Sources

Appl Catal A Gen

J Power Sources

J Mol Catal A Chem

Report of the basic energy sciences workshop on hydrogen production, storage and use

Renewable hydrogen production

Int J Energ Res

Materials for hydrogen storage: current research trends and perspectives

Chem Commun

Interaction of hydrogen with metal nitrides and imides

Nature

Hydrogen storage in high surface area carbon nanotubes produced by catalytic chemical vapor deposition

J Phys Chem B

Room-temperature hydrogen uptake by TiO2 nanotubes

Inorg Chem

Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage

Chem Soc Rev

Synthesis, structural characterization, gas sorption and guest-exchange studies of the lightweight, porous metal-organic framework alpha-[Mg3(O2CH)6]

Inorg Chem

Amine-directed hydroboration: Scope and limitations

J Am Chem Soc

B-N compounds for chemical hydrogen storage

Chem Soc Rev

Will we soon be fueling our automobiles with ammonia-borane?

Angew Chem Int Ed

Ammonia borane the hydrogen source par excellence?

Dalton Trans

A high-performance hydrogen generation system: transition metal-catalyzed dissociation and hydrolysis of ammonia–borane

J Power Sources

Room-temperature hydrogen uptake by TiO₂ nanotubes

Synthesis, structural characterization, gas sorption and guest-exchange studies of the lightweight, porous metal-organic framework alpha-[Mg₃(O₂CH)₆]