Mechanistic Insights into Dehydrogenation of Partially Deuterated Ammonia Borane NH3BD3 Being Heating to 200 °C
Mechanistic Insights into Dehydrogenation of Partially Deuterated Ammonia Borane NH3BD3 Being Heating to 200 °C
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DOI：
10.1021/acs.inorgchem.8b02721
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发表时间：
2019-01-07
影响因子：
4.6
通讯作者：
Demirci, Umit B.
中科院分区：
文献类型：
--
作者：
Petit, Jean-Fabien;Demirci, Umit B.
氨硼NH3BH3是一种众所周知的热分解储氢材料。然而，加热脱氢的机理十分复杂。在此背景下，我们利用热重分析、差示扫描量热法和质谱法研究了固体部分氘化氨硼NH3BD3在200℃下的热解脱氢偶联，即释放第二等量氢。我们的研究结果表明，导致氢（HD）释放的过程主要是由异极性氢-氘相互作用（N-H δ +中心点中心点中心点D δ—B）驱动的。同极性二氢相互作用（N-H δ +中心点中心点中心点H δ +-N）明显有助于氢（即H-2）的释放。相比之下，同极性双氘相互作用（B-D -中心点-中心点-中心点-D -B）的贡献可以忽略不计。综上所述，本研究为热解条件下氨硼烷释放氢的机理提供了新的思路。
Ammonia borane NH3BH3 is a well-known thermolytic hydrogen storage material. However, the mechanism of dehydrogenation under heating is very complex. In this context, we have studied the thermolytic dehydrocoupling of solid, partially deuterated, ammonia borane NH3BD3 up to 200 degrees C, that is, up to the release of the second equivalent of hydrogen, by using thermogravimetric analysis, differential scanning calorimetry, and mass spectrometry. Our results show that the process, resulting in the release of hydrogen (i.e., HD), is mainly driven by heteropolar hydrogen-deuterium interactions (N-H delta+center dot center dot center dot D delta--B). Homopolar dihydrogen interactions (N-H delta+center dot center dot center dot H delta+-N) appreciably contribute to hydrogen (i.e., H-2) release. In contrast, the contribution of homopolar dideuterium interactions (B-D delta-center dot center dot center dot D delta--B) is negligible. In summary, this work sheds new light on the mechanism governing the release of hydrogen from ammonia borane under thermolytic conditions.