Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation
Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation
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DOI：
10.1039/c9sc00731h
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发表时间：
2019-06-28
期刊：
影响因子：
8.4
通讯作者：
Horike, Satoshi
中科院分区：
文献类型：
--
作者：
Kadota, Kentaro;Nghia Tuan Duong;Horike, Satoshi
由于氢化物（H-）具有强的供电子能力和与质子物种的反应性，因此控制其在晶体结构中的反应性一直是一个挑战。对于金属硼氢化物，脱氢活性和空气稳定性处于权衡之中，并且要求控制BH 4-的反应性。为此，我们合成了一系列基于BH 4-的配位聚合物/金属有机框架。BH 4-在结构中的反应性由配位几何形状和相邻配体调节，并且化合物之一[Zn（BH 4）（2）（二吡啶基丙烷）]表现出高脱氢反应性（179 ℃下1.4wt%）和高空气稳定性（25 ℃下50 RH%，7天）。单晶X射线衍射分析表明，H δ +MIDLINE HORIZONTAL ELLIPSISH δ-二氢相互作用和疏水配体的紧密堆积是反应性和稳定性的关键。通过程序升温脱附、原位同步PXRD和固体核磁共振等手段对脱氢机理进行了研究。
Control of the reactivity of hydride (H-) in crystal structures has been a challenge because of its strong electron-donating ability and reactivity with protic species. For metal borohydrides, the dehydrogenation activity and air stability are in a trade-off, and control of the reactivity of BH4- has been demanded. For this purpose, we synthesize a series of BH4--based coordination polymers/metal-organic frameworks. The reactivity of BH4- in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH4)(2)(dipyridylpropane)] exhibits both high dehydrogenation reactivity (1.4 wt% at 179 degrees C) and high air stability (50 RH% at 25 degrees C, 7 days). Single crystal X-ray diffraction analysis reveals that H delta+MIDLINE HORIZONTAL ELLIPSISH delta- dihydrogen interactions and close packing of hydrophobic ligands are the key for the reactivity and stability. The dehydrogenation mechanism is investigated by temperature-programmed desorption, in situ synchrotron PXRD and solid-state NMR.