Thermal decomposition of ammonium perchlorate-based molecular perovskite from TG-DSC-FTIR-MS and ab initio molecular dynamics

(H(2)dabco)[NH(4)(ClO(4))(3)] (DAP, dabco = 1,4-diazabicyclo[2.2.2]octane) is a recently synthesized ammonium perchlorate-based molecular perovskite energetic material. The high-symmetry perovskite configuration assembles the oxidant ClO(4)(−) and fuel H(2)dabco(2+) into a compact cubic crystal, realizing a high energy-releasing efficiency. In this study, the thermal decomposition of DAP has been investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) coupled with Fourier transform infrared (FTIR) spectroscopy and mass spectroscopy (MS). The TG-DSC profiles show that DAP has an intense one-stage heat release process with a weight loss of 94.7%. The evolved gas products are identified as H(2)O, CO(2), CO, HCl, HCN, NH(3), HNCO by FTIR spectrum, in which the infrared characteristic peak at 2283 and 2250 cm(−1) is clarified not from N(2)O and assigned to HNCO. The principal products are H(2)O and CO(2) together with significant amounts of HCl, HCN, NH(3) in MS, while few nitrogen oxides and O(2) are detected. The experimental results show that organic components have been the prominent media for the degradation of ClO(4)(−). To refine the mechanism observed in experiment, ab initio molecular dynamics simulations are carried out to reveal the atomistic reaction mechanisms. The decomposition of DAP starts with proton transfer from NH(4)(+) and H(2)dabco(2+) to ClO(4)(−). The deprotonated carbon skeleton is preferable to NH(3) in capturing O atoms, realizing a faster consumption of O atoms. Amounts of H atoms enter the environment being active free radicals, realizing an efficient autocatalytic chain propagation of degradation of ClO(4)(−). The atomistic thermal decomposition reaction mechanism of DAP uncovers the role of organic components in promoting the degradation of ClO(4)(−), which will help improve the synthesis strategy of molecular perovskite energetic materials with improved performance.