Oriented Assembled Prussian Blue Analogue Framework for Confined Catalytic Decomposition of Ammonium Perchlorate

Abstract

The design of highly dispersed active sites of hollow materials and unique contact behavior with the components to be catalyzed provide infinite possibilities for exploring the limits of catalyst capacity. In this study, the synthesis strategy of highly open 3‐dimensional frame structure Prussian blue analogues (CoFe‐PBA) was explored through structure self‐transformation, which was jointly guided by template mediated epitaxial growth, restricted assembly and directional assembly. Additionally, good application prospect of CoFe‐PBA as combustion catalyst was discussed. The results show that unexpected thermal decomposition behavior can be achieved by limiting AP(ammonium perchlorate) to the framework of CoFe‐PBA. The high temperature decomposition stage of AP can be advanced to 283.6 °C and the weight loss rate can reach 390.03% min−1. In‐situ monitoring shows that CoFe‐PBA can accelerate the formation of NO and NO2. The calculation of reaction kinetics proved that catalytic process was realized by increasing the nucleation factor. On this basis, the catalytic mechanism of CoFe‐PBA on the thermal decomposition of AP was discussed, and the possible interaction process between AP and CoFe‐PBA during heating was proposed. At the same time, another interesting functional behavior to prevent AP from caking was discussed.

Hierarchical MOFs with Good Catalytic Properties and Structural Stability in Oxygen‐Rich and High‐Temperature Environments

“…[16][17][18][19] These limitations significantly restrict the research and development of this material in the field of thermal catalysis. However, the thermal decomposition behavior of MOFs can still be effectively utilized, for example, as self-sacrificial templates [16] or through clever use of ligands, [24] as well as through the clever design of structures such as hierarchical [21] or array structures. [20] These approaches have great potential in the field of thermal catalysis.…”

“…The combustion behavior of the propellant significantly impacts the combat capability of the missile. [17,[22][23][24][25] Improving the thermal decomposition behavior of AP (NH 4 ClO 4 ) by incorporating burn rate modifiers with catalytic effects is an effective strategy to enhance the overall performance of the propellant. The research thus far has validated the advantageous catalytic impact of MOFs on the thermal decomposition of AP.…”

Mechanism of Interaction between Ammonium Perchlorate and Aluminum

“…In the LTD stage, the main decomposition products of AP are ammonia (NH 3 ) and perchloric acid (HClO 4 ). They can adsorb on the surface of condensed-phase AP and inhibit its decomposition. , The dissociated NH 3 and HClO 4 then react further in the HTD stage to produce a variety of compounds. The peak temperature of high-temperature decomposition ( T HTD ) is an essential parameter to characterize the thermal decomposition behavior of AP, and reducing the value of this parameter can effectively increase the propellant burning rate …”

ZIF-8 derived ZnO: a facile catalyst for ammonium perchlorate thermal decomposition

“…These metal complexes decompose at very low temperatures (ahead of AP) leaving metal oxides in the system that will further catalyze AP thermolysis by increased availability of active oxygen and faster oxidation of N to NO, NO 2 and N 2 O. 22,23 Zeolitic imidazole frameworks (ZIFs)a subfamily of MOFs, have recently been in the limelight due to their excellent properties. ZIF-8 (zinc-based MOF) calcination is regarded as the simplest technique to yield crystalline, porous ZnO, which offers more active sites and faster absorption of reaction molecules onto the surface.…”