Role of Hydrogen Abstraction Reaction in Photocatalytic Decomposition of High Energy Density Materials

Abstract

Explosive phenomena includes a stunningly wide range of diverse manifestations, such as supernova remnant shocks and solar flares, violent decomposition chemistry and synthesis of superior materials under extreme conditions, weapons, missiles, and high velocity impact damage, fuels for space rocket engines, festive fireworks, and applications of detonation waves in construction industry and microshocks in medicine. With the earliest stages of explosives chemistry in energetic materials remaining poorly understood and constantly posing new science questions, an achievement of a controllable initiation of detonation process represents a particular challenge. Precise tuning of sensitivity to initiation of detonation via photoexcitation appears unreachable because all known secondary explosives are wide band gap insulators. This research demonstrates how YAG:Nd laser irradiation triggers explosive decomposition of PQ−PETN composites formed by pentaerythritol tetranitrate (PETN), high energy density material, mixed with photosensitive 9,10phenanthrenequinone (PQ). We suggest, explore, and validate a feasible mechanism of photocatalytic decomposition of explosives activated by the laser excitation with the energy of 1.17−2.3 eV and the wavelength of 1064−532 nm.

Iron and Copper Doped Zinc Oxide Nanopowders as a Sensitizer of Industrial Energetic Materials to Visible Laser Radiation

“…This comparison allowed us to assume a significant contribution of the photochemical mechanism in the initiation process of PETN-ZnO:Cu and PETN-ZnO:Fe composites via the second harmonic of the Nd:YAG laser. Previously studied photochemical sensitizing additives, such as 9,10-phenanthrenequinone and magnesium oxide powder, also demonstrated a markedly lower efficiency in the initiation threshold [ 23 , 24 ].…”

“…Photocatalytic chemical reactions are widely applied to solve various technical tasks in various fields such as modern green energy, water purification, organic synthesis, and medicine [ 15 , 16 , 17 , 18 , 19 ]. The role of photochemical processes in the laser initiation of an EM has been discussed since the first publications on this topic [ 20 ] and is still relevant today [ 21 , 22 , 23 , 24 , 25 ]. The key property of radiation is its ability to transfer the energetic material molecule to an excited state from which the decomposition process can occur with no or a lower potential barrier.…”

“…In this case, an effective sensitizing additive should act as a mediator in the transfer of excitation to the EM but should not increase the absorption index of the energy composite to high values. Specific compounds [ 21 , 23 , 25 ] with a particularised mechanism of action and simple inorganic materials without special treatment [ 24 , 26 ] can be applied as photosensitizers.…”

Thermal Decomposition of Gas-Phase Bis(1,2,4-oxadiazole)bis(methylene) Dinitrate (BODN): A CCSD(T)-F12/DFT-Based Study of Reaction Pathways

“…Because INT194 and INT123 only have bonds involving sp 2 - or sp-hybridized multielectron atoms, the rate of decomposition via most unimolecular steps at temperatures of interest was considered likely to be negligible. Therefore, knowing that H-atom abstraction reactions play an important role in the decomposition of other energetic materials (see refs , ), we postulated various possibilities, and for completeness, we considered H-atom abstraction from BODN, INT241, and INT170 as well.…”