Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions
Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions
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DOI：
10.1039/c2dt11867j
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发表时间：
2012-01-01
影响因子：
4
通讯作者：
Ozkar, Saim
中科院分区：
文献类型：
--
作者：
Karahan, Senem;Zahmakiran, Mehmet;Ozkar, Saim
安全高效的储氢是氢作为能源载体的主要障碍。因此，化学储氢新材料的开发一直是人们关注的焦点。特别重要的是，联氨硼烷（N2H4BH3）由于其高重量储氢容量（15.4 wt%）和低分子量而成为最有前途的固体氢载体之一。本文报道了在温和条件下，金属催化硼合肼（N2H4BH3， HB）的甲醇分解作为一种快速制氢体系。将微量氯化镍（NiCl2）加入到硼肼甲醇溶液（[HB]/[Ni] >= 200）中，反应溶液在室温下以24 mol H-2 (mol Ni min)（-1）的速率释放3等量的H-2。本文报告的结果还包括：(i)利用ATR-IR、DP-MS、H-1和B-11 NMR光谱技术鉴定反应产物并建立反应化学计量学；（ii）研究底物和催化剂浓度对产氢速率的影响，确定硼肼催化甲醇分解的速率规律；（iii）确定活化参数(E-a、Delta H-#、和Delta S-#)，利用产氢速率的温度依赖性数据，对硼烷肼进行催化甲醇分解。
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.