A Systematic Study of the Effects of Metal Chloride Additives on H2 Desorption Properties of Ammonia Borane
A Systematic Study of the Effects of Metal Chloride Additives on H2 Desorption Properties of Ammonia Borane
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DOI：
10.1021/acs.jced.6b00143
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发表时间：
2016-04
影响因子：
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通讯作者：
Y. Nakagawa;Tengfei Zhang;M. Kitamura;S. Isobe;S. Hino;N. Hashimoto;S. Ohnuki
中科院分区：
文献类型：
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作者：
Y. Nakagawa;Tengfei Zhang;M. Kitamura;S. Isobe;S. Hino;N. Hashimoto;S. Ohnuki
系统地研究了多种元素在氨基硼烷(AB)中的掺杂效果。选用第4期纯过渡金属和17种金属氯化物作为添加剂，用AB球磨。金属氯化物添加剂可以有效地降低氢气的脱附温度和副产物气体的排放量，而纯过渡金属由于不起Lewis酸的作用而没有表现出任何作用。观察到氢的脱附温度与金属的鲍林电负性(χp)有很强的相关性。MCln中的Mn+可作为Lewis酸引发AB脱氢偶联反应。NH3的释放量与M的离子半径相关，表明在该体系中形成了MCln·mNH3络合物。AB-CuCl2和AB-AgCl2混合物表现出相似的H2脱附过程。在反应过程中，含氯中间相会破坏AB的稳定性。
The effects of metal-based additives in a wide range of elements doping into ammonia borane (AB) were systematically investigated. Pure transition metals in period 4 and total of 17 metal chlorides were selected as additives and ball-milled with AB. Metal chloride additives were effective to decrease H2 desorption temperature and the amounts of byproduct gas emissions of AB, whereas pure transition metals did not show any ability because they did not work as Lewis acids. The strong correlation between H2 desorption temperature and the Pauling electronegativity of metal (χp) was observed. Mn+ of MCln would work as Lewis acid to initiate the AB dehydrocoupling reaction. The amount of NH3 emission was correlated with the ionic radius of M, suggesting MCln·mNH3 complexes be formed in this system. AB–CuCl2 and AB–AgCl mixtures showed the similar H2 desorption processes. The Cl-containing intermediate phase would destabilize AB during reaction.