Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey.
Dalton Trans. 2012 Apr 28;41(16):4912-8. doi: 10.1039/c2dt11867j.
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 (N(2)H(4)BH(3)) 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 (N(2)H(4)BH(3), HB) as a fast hydrogen generation system under mild conditions. When trace amounts of nickel(ii) chloride (NiCl(2)) 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, (1)H and (11)B 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), ΔH(#), and ΔS(#)) for the catalytic methanolysis of hydrazine borane by using the temperature dependent rate data of the hydrogen generation.
安全高效的储氢是将氢气作为能源载体的主要障碍。因此，人们集中精力开发用于化学储氢的新材料。特别重要的是，由于肼基硼烷（N（2）H（4）BH（3））具有高重量比氢存储容量（15.4wt%）和低分子量，因此作为最有前途的固体氢载体之一而受到关注。在此，我们报告了在温和条件下金属催化甲醇解肼基硼烷（N（2）H（4）BH（3），HB）作为快速制氢体系。当痕量的二氯化镍（NiCl（2））添加到肼基硼烷的甲醇溶液中（[HB]/[Ni]≥200）时，反应溶液在室温下以 24mol H（2）（mol Ni min）（-1）的速率释放 3 当量的 H（2）。这里报道的结果还包括（i）通过使用 ATR-IR、DP-MS、（1）H 和（11）B NMR 光谱技术以及建立反应化学计量来鉴定反应产物，（ii）研究底物和催化剂浓度对制氢速率的影响，以确定肼基硼烷催化甲醇解的反应动力学，（iii）通过使用生成氢气的温度相关速率数据确定肼基硼烷催化甲醇解的活化参数（E（a），ΔH（#）和ΔS（#））。
