TY - JOUR
T1 - Energetic Metal-Organic Frameworks Incorporating NH3OH+ for New High-Energy-Density Materials
AU - Feng, Yongan
AU - Chen, Sitong
AU - Deng, Mucong
AU - Zhang, Tonglai
AU - Zhang, Qinghua
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/9/16
Y1 - 2019/9/16
N2 - Energetic metal-organic frameworks (E-MOFs) have witnessed increasing development over the past several years. However, as a highly energetic cation, NH3OH+ has never been explored to construct transition-metal-based E-MOFs. Herein, we report the first examples of NH3OH+-containing E-MOFs with bis(tetrazole)methane (H2btm) as a ligand and copper and manganese as central metal ions, [(NH3OH)2(Cu(btm)2)]n and [(NH3OH)2(Mn(btm)2)]n. 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 (Tdec = 230.3 °C), which surpasses those of known NH3OH+-containing compounds. They also have high energy density; in particular, the Cu-based E-MOF affords a high heat of combustion (11447 kJ kg-1) and high heat of detonation (713.8 kJ mol-1) 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.
AB - Energetic metal-organic frameworks (E-MOFs) have witnessed increasing development over the past several years. However, as a highly energetic cation, NH3OH+ has never been explored to construct transition-metal-based E-MOFs. Herein, we report the first examples of NH3OH+-containing E-MOFs with bis(tetrazole)methane (H2btm) as a ligand and copper and manganese as central metal ions, [(NH3OH)2(Cu(btm)2)]n and [(NH3OH)2(Mn(btm)2)]n. 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 (Tdec = 230.3 °C), which surpasses those of known NH3OH+-containing compounds. They also have high energy density; in particular, the Cu-based E-MOF affords a high heat of combustion (11447 kJ kg-1) and high heat of detonation (713.8 kJ mol-1) 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.
UR - http://www.scopus.com/inward/record.url?scp=85072234367&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b01636
DO - 10.1021/acs.inorgchem.9b01636
M3 - 文章
C2 - 31483616
AN - SCOPUS:85072234367
SN - 0020-1669
VL - 58
SP - 12228
EP - 12233
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -