Institute of Chemical Materials , China Academy of Engineering Physics (CAEP) , Mianyang , 621900 , People's Republic of China.
School of Mechatronical Engineering , Beijing Institute of Technology , Beijing 100081 , People's Republic of China.
Inorg Chem. 2019 Sep 16;58(18):12228-12233. doi: 10.1021/acs.inorgchem.9b01636. Epub 2019 Sep 4.
Energetic metal-organic frameworks (E-MOFs) have witnessed increasing development over the past several years. However, as a highly energetic cation, NHOH has never been explored to construct transition-metal-based E-MOFs. Herein, we report the first examples of NHOH-containing E-MOFs with bis(tetrazole)methane (Hbtm) as a ligand and copper and manganese as central metal ions, [(NHOH)(Cu(btm))] and [(NHOH)(Mn(btm))]. Crystal structure determinations reveal that both E-MOFs show two-dimensional layered structures. Experimental results suggest that they have high thermal decomposition temperatures (>200 °C). Among them, Cu-based E-MOFs possesses outstanding thermal stability ( = 230.3 °C), which surpasses those of known NHOH-containing compounds. They also have high energy density; in particular, the Cu-based E-MOF affords a high heat of combustion (11447 kJ kg) and high heat of detonation (713.8 kJ mol) beyond the most powerful organic explosives in use today. Additionally, the two E-MOFs show completely different sensitivity properties: the Mn-based E-MOF is an insensitive high-energy-density material (IS > 40 J; FS > 360 N; EDS > 20 J), while the Cu-based E-MOF can be classified as a sensitive energetic material (IS = 13 J; FS = 216 N; EDS = 10.25 J), demonstrating their diverse applications in different fields. Our research proposes a unique class of high-energy-density materials.
含氨基羟基金属有机框架材料的研究进展
含能金属有机框架材料（E-MOFs）近年来得到了快速发展。然而，作为一种高能阳离子，NHOH 从未被用于构建过渡金属基 E-MOFs。在此，我们报告了首例含 NHOH 的 E-MOFs，其配体为双（四唑）甲烷（Hbtm），中心金属离子为铜和锰，分别为[（NHOH）（Cu（btm））]和[（NHOH）（Mn（btm））]。晶体结构测定表明，两种 E-MOFs 均具有二维层状结构。实验结果表明，它们具有较高的热分解温度（＞200°C）。其中，基于 Cu 的 E-MOF 具有出色的热稳定性（Td = 230.3°C），超过了已知的含 NHOH 化合物。它们还具有较高的能量密度；特别是，基于 Cu 的 E-MOF 具有较高的燃烧热（11447 kJ kg）和爆轰热（713.8 kJ mol），超过了目前使用的最强大的有机炸药。此外，两种 E-MOFs 表现出完全不同的感度特性：基于 Mn 的 E-MOF 是一种不敏感的高能密度材料（IS＞40 J；FS＞360 N；EDS＞20 J），而基于 Cu 的 E-MOF 可归类为敏感的含能材料（IS = 13 J；FS = 216 N；EDS = 10.25 J），这表明它们在不同领域具有多样化的应用前景。我们的研究提出了一类独特的高能密度材料。
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