Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions

Karahan, Senem
Zahmakıran, Mehmet
Özkar, Saim
Safe and efficient hydrogen storage is a major obstacle for using hydrogen as an energy carrier. Therefore, intensive efforts have been focused on the development of new materials for chemical hydrogen storage. Of particular importance, hydrazine borane (N2H4BH3) is emerging as one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (15.4 wt%) and low molecular weight. Herein, we report metal catalyzed methanolysis of hydrazine borane (N2H4BH3, HB) as a fast hydrogen generation system under mild conditions. When trace amounts of nickel(II) chloride (NiCl2) is added to the methanol solution of hydrazine borane ([HB]/[Ni] >= 200) the reaction solution releases 3 equiv. of H-2 with a rate of 24 mol H-2 (mol Ni min)(-1) at room temperature. The results reported here also includes (i) identification of the reaction products by using ATR-IR, DP-MS, H-1 and B-11 NMR spectroscopic techniques and the establishment of the reaction stoichiometry, (ii) investigation of the effect of substrate and catalyst concentrations on the hydrogen generation rate to determine the rate law for the catalytic methanolysis of hydrazine borane, (iii) determination of the activation parameters (E-a, Delta H-#, and Delta S-#) for the catalytic methanolysis of hydrazine borane by using the temperature dependent rate data of the hydrogen generation.


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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 [261 has sho...
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Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 +/- 0.9 n...
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Hydrogen storage is one of the attractive research interests in recent years due to the advantages of hydrogen to be used as energy source. The studies on hydrogen storage applications focus mainly on investigation of hydrogen storage capabilities of newly introduced compounds. The present paper aims at characterization of CaXH3 (X: Mn, Fe, or Co) perovskite-type hydrides for the first time to understand their potential contribution to the hydrogen storage applications. CaXH3 compounds have been investigate...
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Production of hydrogen, which has been considered as an environmentally clean ideal energy carrier, from abundant energy resources cleanly and renewably is essential to support sustainable energy development. Hydrogen production from bio-ethanol by steam reforming process is a promising approach, since bio-ethanol is the most available bio-fuel in the world and steam reforming of ethanol yields formation of 6 moles of hydrogen per mole of ethanol. Support material used for nickel based catalysts plays a cru...
Citation Formats
S. Karahan, M. Zahmakıran, and S. Özkar, “Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions,” DALTON TRANSACTIONS, pp. 4912–4918, 2012, Accessed: 00, 2020. [Online]. Available: