Single Cu Atoms Anchored Energetic COFs as Combustion Catalytic Promoters toward Rapid and Concentrated Thermal Decomposition of Ammonium Perchlorate

Achieving a synergistic, rapid, and concentrated energy release process of ammonium perchlorate (AP) is of vital significance for boosting the thrust of composite solid propellants. However, conventional catalytic promoters often exhibit suboptimal catalytic kinetics due to inefficient utilization of active sites. Herein, atomically dispersed Cu-coordinated covalent organic frameworks (COFs)-based catalytic promoters are reported, decorating with energetic anion groups. The highly accessible single Cu sites confined in the COFs significantly contribute to the raid and concentrated energy release of AP, yielding a sharply narrowed decomposition peak at 341.3 °C with a peak width of only 9 °C. This performance is markedly superior to the dispersed exothermic process of raw AP (410.3 °C with a peak width of 30 °C). Additionally, the energetic COF promoter considerably increased the output energy via collaboratively promoting the chemical energy release of AP and its own decomposition. Correlating in situ spectroscopies and theoretical calculations reveals that the incorporated anionic groups effectively modulate the local electronic structure of the Cu sites. This alteration promotes the key step of cleavage of Cl─O bonds in AP intermediates to produce reactive oxygen species and also boosts the oxidation of NH₃ to high-valence nitrogen oxides, thereby accelerating the combustion reaction kinetic.