A new nitrate-based energetic molecular perovskite as a modern edition of black powder
Shao‐Li Chen, Yu Shang, Jun Jiang, Meng Huang, Jia‐Tong Ren, Tao Guo, Chenxi Yu, Wei‐Xiong Zhang, Xiao‐Ming Chen
Abstract
In recent years, energetic molecular perovskites, which serve as an energetic material design platform, have shown potential for designing primary and secondary explosives. To explore their potential in gunpowder and pyrotechnics, this study constructed a new nitrate-bridged molecular perovskite, (H 2 dabco)[K(NO 3 ) 3 ] ( DAN-2 , H 2 dabco 2+ = 1,4-diazabicyclo-[2.2.2.]octane-1,4-diium), based on potassium nitrate—a major component of black powder. The single-crystal structure analysis indicated that DAN-2 possesses a cubic perovskite structure in the space group Pm 3 ¯ m. Theoretical calculations revealed that DAN-2 has an energy level slightly higher than TNT and much higher than black powder. Adding DAN-2 into a typical propellant formulation can increase the impetus while significantly lowering the flame temperature. Moreover, DAN-2 has a lower sensitivity ( IS = 29 J, FS > 360 N) than TNT ( IS = 15 J, FS = 360 N). It is worth mentioning that DAN-2 can avoid the environmental concern of sulfide-induced acid rain since it does not bear any sulfur. Therefore, DAN-2 can be considered a new single explosive and a modern edition of black powder obtained via mixing oxidative KNO 3 and a reductive organic fuel at the molecular scale. Furthermore, it displays promising potential in the field of gunpowder and pyrotechnics. This study synthesized the first nitrate-based molecular perovskite energetic compound (H 2 dabco)[K(NO 3 ) 3 ] ( DAN-2 ), which has an inorganic oxidative framework, consists of the potassium ions and nitrate anions, and can be regarded as the modern edition of black powder obtained through homogeneously mixing oxidative and reductive components containing only “clean” elements at the molecular scale. DAN-2 has a much higher energy level and lower sensitivity than black powder. Moreover, it possesses much more sufficient combustion, thereby avoiding the smoke problem of incomplete combustion caused by mechanical mixing and environmental issues caused by using sulfur in black powder.