Covalent organic frameworks-enabled interfacial engineering of ammonium dinitramide for enhanced stability and energy release

Decoupling the inherent trade-off between energy output, thermal stability, and environmental tolerance remains a central challenge in energetic materials. Ammonium dinitramide (ADN), a high-energy oxidizer with great potential for advanced propulsion systems, is severely limited by moisture sensitivity and insufficient stability. Herein, a COF-based interfacial engineering strategy is developed to simultaneously enhance the stability and energy release behavior of ADN. Conjugated covalent organic frameworks (COFs) layers are in situ constructed on ADN crystals, forming a protective and electronically active shell that improves thermal tolerance and accelerates energy release. The resulting ADN@COFs composites exhibit significantly reduced water uptake and an increase in onset decomposition temperature of up to 25.1 °C, while delivering enhanced combustion performance. Further functionalization with a thin PTFE layer via pore anchoring provides additional hydrophobicity, contributing to moisture resistance without compromising energetic output. Density functional theory (DFT) calculations reveal pronounced interfacial charge redistribution, where the π-conjugated COFs act as an electronic bridge that promotes electron delocalization and facilitates energetic decomposition. This work demonstrates an effective route to regulate energetic performance through interfacial electronic coupling and hierarchical functionalization.