Potassium N‐Nitramino‐5H‐Tetrazolates – Powerful Green Primary Explosives with High Initiation Capabilities

Abstract

Since the nowadays used lead-based primary explosives, lead azide, picrate and styphnate suffer from various environmental and toxic issues, there is a great need for new green materials. Therefore, two highly promising lead-free primary explosives potassium 1-(N-nitramino)-5Htetrazolate (1, 1-KNAT) and potassium 2-(N-nitramino)-5Htetrazolate (2, 2-KNAT) have been synthesized and characterized. Both isomers show superior energetic performance, initiation capability and were comprehensively analyzed by low-temperature X-ray diffraction, IR, multinuclear NMR spectroscopy, elemental analysis, and DTA. Sensitivity determinations toward impact, friction, and electrostatic discharge revealed its highly powerful, but also sensitive character. In addition, their potential as lead-free primaries were evaluated in initiation tests of PETN or RDX filled detonators confirming their great suitability as lead-free primary explosives. Figure 7. A) and B) HN test of 1 and 2; C) and D) HP test of 1 and 2; E) Positive PETN (left) and RDX (right) initiation tests with 5 mg of compound 1 (bottom) and 2 (top).

Chemistry of 2,5-diaminotetrazole

“…1). 11 In addition to the exotic, trisubstituted 1,4,5-triaminotetrazolium cation, which is described as a thermally labile nitrate and nitrotetrazol-2-olate, 12 1,5-diaminotetrazole is the most versatile aminotetrazole representative and is highly recommended in Fig. 1 Compounds with exclusively aminotetrazole functionalities, the gas phase heats of formation (calculated on CBS-4M level of theory) and their respective nitrogen content: 5-aminotetrazole, 1-aminotetrazole, 2-aminotetrazole, 1,5-diaminotetrazole, 2,5-diaminotetrazole (1) and the 1,4,5-triaminotetrazolium cation.…”

Poly Tetrazole Containing Thermally Stable and Insensitive Alkali Metal-Based 3D Energetic Metal–Organic Frameworks

“…24−27 Besides, EMOFs employing alkali metal ions as nodes are more economical and eco-friendly than transition metal/heavy metal ions. 16,28,29 Sodium and potassium ions stick out due to their high coordination ability and endow high density, thermal stability, and mechanical hardness to EMOFs. 16,17,29 However, the known tetrazole-based Na/K energetic MOFs are limited and have gained significant attention, mainly due to their high performance and environmental compatibility.…”

“…16,17,29 However, the known tetrazole-based Na/K energetic MOFs are limited and have gained significant attention, mainly due to their high performance and environmental compatibility. 16,17,28,29 Na-based energetic MOFs, such as [Na(H 2 BTT) (H 2 O) 2 ] n (a), 16 [Na(atza)] n (b), and [Na 2 (tza)] n (c), 17 represented a substantial improvement in thermal stability and insensitivity with low detonation performances (Figure 1), while KNAT 28 and K 2 DNABT 30 were sensitive and less thermally stable. 28,30,31 In this regard, herein, we have synthesized two new nitrogen-and oxygen-rich EMOFs, [Na 3 (L) 3 (H 2 O) 6 ] n (1) and [K 3 (L) 3 (H 2 O) 3 ] n (2), by the facile synthetic route.…”

“…16,17,28,29 Na-based energetic MOFs, such as [Na(H 2 BTT) (H 2 O) 2 ] n (a), 16 [Na(atza)] n (b), and [Na 2 (tza)] n (c), 17 represented a substantial improvement in thermal stability and insensitivity with low detonation performances (Figure 1), while KNAT 28 and K 2 DNABT 30 were sensitive and less thermally stable. 28,30,31 In this regard, herein, we have synthesized two new nitrogen-and oxygen-rich EMOFs, [Na 3 (L) 3 (H 2 O) 6 ] n (1) and [K 3 (L) 3 (H 2 O) 3 ] n (2), by the facile synthetic route. Single crystal X-ray diffraction (SCXRD) analysis manifests that compounds 1 and 2 exhibits a 3D framework.…”

“…In recent years, several of them have been reported to have less sensitivity and notable energetic performance due to their stable extensive grids. − However, it is crucial to screen an energetic ligand with good performance as it can endow high detonation performance of energetic MOFs. Due to the large nitrogen percentage, heterocyclic azole-based energetic ligands, such as pyrazole, imidazole, triazole, and tetrazole, were preferred due to their high bond energies: C–N (273 kJ/mol), N–N (160 kJ/mol), NN (418 kJ/mol), and NN (954 kJ/mol). , Among all, tetrazole is highly preferred due to its high energy content. − Besides, EMOFs employing alkali metal ions as nodes are more economical and eco-friendly than transition metal/heavy metal ions. ,, Sodium and potassium ions stick out due to their high coordination ability and endow high density, thermal stability, and mechanical hardness to EMOFs. ,, However, the known tetrazole-based Na/K energetic MOFs are limited and have gained significant attention, mainly due to their high performance and environmental compatibility. ,,, Na-based energetic MOFs, such as [Na­(H 2 BTT) (H 2 O) 2 ] n (a), [Na­(atza)] n (b), and [Na 2 (tza)] n (c), represented a substantial improvement in thermal stability and insensitivity with low detonation performances (Figure ), while KNAT and K 2 DNABT were sensitive and less thermally stable. ,, …”