The synthesis of energetic metal–organic frameworks (EMOFs) with one-dimensional, two-dimensional and three-dimensional structures is an effective strategy for developing new-generation high-energy-density and insensitive materials. The basic properties, models, synthetic strategies and applications of EMOF materials with nitrogen-rich energetic groups as ligands are reviewed. In contrast with traditional energetic materials, EMOFs exhibit some interesting characteristics, like tunable structure, diverse pores, high-density, high-detonation heat and so on. The traditional strategies to design EMOF materials with ideal properties are just to change the types and the size of energetic ligands and to select different metal ions. Recently, some new design concepts have come forth to produce more EMOFs materials with excellent properties, by modifying the energetic groups on the ligands and introducing highly energetic anion into skeleton, encapsulating metastable anions, introducing templates and so on. The paper points out that appropriate constructing strategy should be adopted according to the inherent characteristics of different EMOFs, by combining with functional requirements and considering the difficulties and the cost of production. To promote the development and application of EMOF materials, the more accurate and comprehensive synthesis, systematic performance measurement methods, theoretical calculation and structure simulation should be reinforced.

Bamboo leaf-like CuO(b) and flaky-shaped CuO(f) were prepared by the hydrothermal method, and then combined with Al nanoparticles to form Al/CuO(b) and Al/CuO(f) by the ultrasonic dispersion method. The phase, composition, morphology, and structure of the composites were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy scattering spectrometer (EDS). The compatibility of CuO, Al/CuO and nitrocellulose (NC) was evaluated by differential scanning calorimetry (DSC). The effects of CuO and Al/CuO on the thermal decomposition of NC were also studied. The results show that the thermal decomposition reactions of CuO-NC composite, Al/CuO-NC composite, and NC follow the same kinetic mechanism of Avrami-Erofeev equation. In the cases of CuO and Al/CuO, they could promote the O-NO₂ bond cleavage and secondary autocatalytic reaction in condensed phase. The effects of these catalysts have some difference in modifying the thermolysis process of NC due to the microstructures of CuO and the addition of Al nanopowders. Furthermore, the presence of Al/CuO(f) can make the Al/CuO(f)-NC composite easier to ignite, whereas the composites have strong resistance to high temperature. Compatibility and thermal safety analysis showed that the Al/CuO had good compatibility with NC and it could be used safely. This contribution suggests that CuO and Al/CuO played key roles in accelerating the thermal decomposition of NC.

The fiber-like bis-(dimethylglyoximato) nickel(II) complex, Ni(DMG)₂ was successfully synthesized. The obtained samples were characterized by SEM-EDS, FT-IR, XRD, and XPS. The TG-DSC-FTIR-MS coupling technique was used to characterize the thermal decomposition behavior and evolved gas analysis of Ni(DMG)₂. The non-isothermal decomposition reaction kinetic parameters were obtained by both combined kinetic analysis and isoconversional Vyazovkin methods. It was found that Ni(DMG)₂ begins to decompose at around 280 °C, and a sharp exothermic peak is observed in the DSC curve at about 308.2 °C at a heating rate of 10 °C·min⁻¹. The main gaseous products are H₂O, NH₃, N₂O, CO, and HCN, and the content of H₂O is significantly higher than that of the others. The activation energy obtained by the combined kinetic analysis method is 170.61 ± 0.65 kJ·mol⁻¹. The decomposition process can be described by the random nucleation and growth of the nuclei model. However, it was challenging to attempt to evaluate the reaction mechanism precisely by one ideal kinetic model.

The crystal structure has a great influence on mechanical sensitivity and detonation performance of energetic materials. An efficient microfluidic platform was applied for size, morphology, and crystallinity controllable preparation of ultrafine HMX. The microfluidic platform has good mixing performance, quick response, and less reagent consumption. The ultrafine γ-HMX was first prepared at room temperature by microfluidic strategy, and the crystal type can be controlled accurately by adjusting the process parameters. With the increase in flow ratio, the particle size decreases gradually, and the crystal type changed from β-HMX to γ-HMX. Thermal behavior of ultrafine HMX shows that γ→δ is easier than β→δ, and the phase stability of HMX is β > γ > δ. Furthermore, the ultrafine β-HMX has higher thermal stability and energy release efficiency than that of raw HMX. The ultrafine HMX prepared by microfluidic not only has uniform morphology and narrow particle size distribution, but also exhibits high density and low sensitivity. This study provides a safe, facile, and efficient way of controlling particle size, morphology, and crystallinity of ultrafine HMX.

1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) is a type of high energy explosive, its application in weapon systems is limited by its high mechanical sensitivity. At the same time, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a famous insensitive explosive. The preparation of RDX@FOX-7 composites can meet the requirements, high energy and low sensitivity, of the weapon systems. It is difficult for the reactor to achieve uniform quality of composite material, which affects its application performance. Based on the principle of solvent-anti-solvent, the recrystallization process was precisely controlled by microfluidic technology. The RDX@FOX-7 composites with different mass ratios were prepared. At the mass ratio of 10%, the RDX@FOX-7 composites are ellipsoid of about 15 μm with uniform distribution and quality. The advantages of microscale fabrication of composite materials were verified. The results of structure characterization showed that there is no new bond formation in RDX@FOX-7, but the distribution of two components on the surface of the composite was uniform. Based on the structure characterization, we established the structure model of RDX@RDX-7 and speculated the formation process of the composites in microscale. With the increase of FOX-7 mass ratios, the melting temperature of RDX was advanced, the thermal decomposition peak of RDX changed to double peaks, and the activation energy of RDX@FOX-7 composite decreased. These changes were more pronounced between 3 and 10% but not between 10 and 30%. The ignition delay time of RDX@FOX-7 was shorter than that of RDX and FOX-7. RDX@FOX-7 burned more completely than RDX indicating that FOX-7 can assist heat transfer and improve the combustion efficiency of RDX.

Structural regulation is of great significance for improving the comprehensive performance of energetic materials (EMs). The structural regulation and properties of EMs were summarized. For single-component EMs, particle size control focuses on quality consistency and industrial scalability, morphology modification mainly improves sphericity through monomers or aggregates and explores the possibility of layered energetic materials in improving mechanical properties, and polycrystalline regulation suppresses metastable phases and explores novel crystalline forms using simulation-guided design. Composite EMs (CEMs) employ core–shell structures to balance safety with performance via advanced coating materials, cocrystal engineering to tailor energy release through intermolecular interactions, and lattice strain modulation, and mixing structures integrates component advantages while enhancing the reaction efficiency. Future directions emphasize computational simulations and novel fabrication methods to guide the rational design and precise preparation of next-generation EMs with specific functions.