New Insights into the Catalytic Decomposition of Ammonium Perchlorate and Decomposition Mechanism by Nano‐CuO Dispersed in Graphite‐Carbon Nitride Nanosheet Composites

Abstract

Enhancing the exothermic decomposition of ammonium perchlorate (AP) is of great significance to obtain solid propellants with excellent combustion performance. Herein, we prepared a series of composites for catalyzing the exothermic decomposition of AP by a facile method with different masses of nano copper oxide (n-CuO) dispersed in graphene-nitride carbon (g-C 3 N 4 ) nanosheets. Among them, n-CuO-8/g-C 3 N 4 showed the best catalytic activity, which reduced the high-temperature decomposition (HTD) value by 95.0 °C, and increased the total heat release by 505 J • g À 1 . The n-CuO-12/g-C 3 N 4 also reduced the activation energy (E a ) of the HTD stage by 47.34 kJ • mol À 1 . The catalytic mechanism study suggested that the n-CuO-X/g-C 3 N 4 composites promoted the transition of electrons (e À ) and holes (h + ) from ClO 4À to NH 4 + and inhibited the recombination of e À and h + , which further enhanced the exothermic decomposition of AP. During decomposition, the transformation of N 2 O to NO was significantly inhibited by the n-CuO-X/g-C 3 N 4 composites, thus increasing the integral heat release as evidenced by Real-time thermogravimetry/Fourier transform infrared spectroscopy. This study illustrated that n-CuO-X/g-C 3 N 4 composites are catalysts for the efficient decomposition of AP, which further enhance the energy performance of solid propellants.

Carbon‐Nitride Popcorn—A Novel Catalyst Prepared by Self‐Propagating Combustion of Nitrogen‐Rich Triazenes

“…It was found that in all these AP formulations, no significant effect was observed on the first stage of the endothermic polymorphic transition in AP, which is in agreement with other reported catalysts for the AP decomposition. [ 73–76 ] In contrast, the second and third exothermic stages of the AP's decomposition were significantly affected in formulations containing compounds 1, 3–7 and PCN5, with both exotherms merging into a single exothermic peak. More specifically, these single exothermic peaks were observed (onset temperatures) at 335 °C (compound 1), 311 °C (compound 3), 309 °C (compound 4), 300 °C (compound 5), 302 °C (compound 6), 296 °C (compound 7), and 317 °C (PCN5) (Figures S55–S72, Supporting Information).…”

“…A similar process was previously reported as a plausible mechanism for the thermal decomposition of AP‐g‐C 3 N 4 formulations. [ 74–121 ]…”

“…[27,69] A particularly interesting application for PCN derived materials that attracted a significant attention in recent years is their utilization in aerospace propulsion systems, as a catalyst for the decomposition of ammonium perchlorate (AP) oxidizer, which is a critical and major component in solid propellants. [70][71][72] A number of modified g-C 3 N 4 materials, such as CuO/g-C 3 N 4 , [73,74] nano-Cu/Cu 2 O dispersed on g-C 3 N 4 , [75,76] TeO 2 or SnO 2 nanoparticle containing g-C 3 N 4 , [77,78] Fe, Nd, Ce, Zr, and U-doped g-C 3 N 4 , [79] g-C 3 N 4 /reduced graphene oxide/ layered MnO 2 , [80] and CeO 2 /g-C 3 N 4 [81] were reported to work as burn rate modifiers, functioning by lowering down the decomposition temperature and activation energy of AP, accompanied by a higher energy release. In contrast to a plethora of g-C 3 N 4based AP-decomposition catalysts, to the best our knowledge, there are no reports regarding PCNs with other C-to-N ratios that were evaluated for this catalytic activity.…”

Effects of Barium‐Copper‐Cobalt oxide composites supported on reduced graphene oxide in the thermolysis of ammonium perchlorate and 3‐nitro‐1,2,4‐triazol‐5‐one

“…The presence of BCC/rGO composite plays an important role in terms of following both mechanism redox and electron transfer that gives the fast acceleration of energetic molecules to decompose. [46,47] Thus, such multifunctional materials can be useful for the preparation of chemical propulsion systems for rocketry purposes. Lei et al [48] have reported the effect of transition metal complexes based on Co, Ni, and Cu on the thermal decomposition of AP.…”