Study of the thermal decomposition mechanism of FOX-7 by molecular dynamics simulation and online photoionization mass spectrometry

The thermal decomposition mechanism of energetic materials is important for analyzing the combustion mechanisms of propellants and evaluating the safety of propellants during transport and storage. 1,1-Diamino-2,2-dinitroethylene (FOX-7) is an important insensitive energetic material that can be used as an oxidizer in propellants. However, the initial decomposition mechanism of FOX-7 is not clear to date. The ReaxFF molecular dynamics method is widely used in the investigation of the thermal decomposition mechanisms of energetic materials. Meanwhile, the combination of thermogravimetry with online photoionization time-of-flight mass spectrometry (TG-PI-TOF-MS) and online single-photon ionization time-of-flight mass spectrometry (SPI-TOF-MS) can reveal the decomposition products, which may be integrated with the results of the simulation. In this study, the primary thermal decomposition mechanism of 1,1-diamino-2,2-dinitroethylene (FOX-7) was studied by the ReaxFF molecular dynamics simulations and online photoionization mass spectrometry. The results of the molecular dynamics simulations showed that the primary decomposition step of FOX-7 is C–NO(2) cleavage; after this, C[double bond, length as m-dash]O formation occurs via a three-membered ring transition state, followed by NO elimination. The remaining structure loses NH(2) and H, resulting in the formation of the NHC[double bond, length as m-dash]C[double bond, length as m-dash]O structure, which finally breaks down into HNC and CO. NH(2) reacts with an H atom to produce NH(3). A reversible intramolecular hydrogen transfer was also observed at 2500 K; however, it failed to dominate the decomposition reaction. During the decomposition of FOX-7, the major products are N(2), NH(3), CO(2), and H(2)N(2) and the minor products are H(2)O, HN(2), and H(2). The TG-PI-TOF-MS spectrum shows three signals, i.e., m/z = 18, 28, and 30, which can be assigned to H(2)O, CO, and NO, respectively. Moreover, four signals at m/z = 72.72, 55.81, 45.79, and 29.88 corresponding to the products (NH(2))(2)C[double bond, length as m-dash]C[double bond, length as m-dash]O, (NH(2))C[double bond, length as m-dash]C[double bond, length as m-dash]O, NO(2), and NO have been obtained in the SPI-TOF-MS spectrum. The experimental data obtained via online photoionization mass spectrometry further validated the results of the molecular dynamics simulations.