碱金属和碱土金属氨基硼烷：结构、晶体化学及储氢性能。

Alkali and alkaline-earth metal amidoboranes: structure, crystal chemistry, and hydrogen storage properties.

作者信息

Wu Hui, Zhou Wei, Yildirim Taner

机构信息

NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, USA.

出版信息

J Am Chem Soc. 2008 Nov 5;130(44):14834-9. doi: 10.1021/ja806243f. Epub 2008 Oct 11.

DOI:10.1021/ja806243f

PMID:18847204

Abstract

Alkali- and alkaline-earth metal amidoboranes are a new class of compounds with rarely observed NH2BH3 units. LiNH2BH3 and solvent-containing Ca(NH2BH3)2 x THF have been recently reported to significantly improve the dehydrogenation properties of ammonia borane. Therefore, metal amidoboranes, with accelerated desorption kinetics and suppressed toxic borazine, are of great interest for their potential applications for hydrogen storage. In this work, we successfully determined the structures of LiNH2BH3 and Ca(NH2BH3)2 using a combined X-ray diffraction and first-principles molecular dynamics simulated annealing method. Through detailed structural analysis and first-principles electronic structure calculations the improved dehydrogenation properties are attributed to the different bonding nature and reactivity of the metal amidoboranes compared to NH3BH3.

摘要

碱金属和碱土金属氨基硼烷是一类新型化合物，含有罕见的[NH₂BH₃]⁻单元。最近有报道称，LiNH₂BH₃和含溶剂的Ca(NH₂BH₃)₂·THF能显著改善氨硼烷的脱氢性能。因此，金属氨基硼烷具有加速的解吸动力学和抑制的有毒硼嗪，因其在储氢方面的潜在应用而备受关注。在这项工作中，我们使用X射线衍射和第一性原理分子动力学模拟退火相结合的方法成功确定了LiNH₂BH₃和Ca(NH₂BH₃)₂的结构。通过详细的结构分析和第一性原理电子结构计算，与NH₃BH₃相比，金属氨基硼烷改善的脱氢性能归因于其不同的键合性质和反应活性。