Energetic Metal–Organic Frameworks With Enhanced Catalytic Performance for Ammonium Perchlorate Thermal Decomposition

Abstract

ABSTRACT Ammonium perchlorate (AP), the pivotal oxidizer in composite solid propellants, is often constrained due to its high decomposition temperature and sluggish heat release. Here, we proposed a structural co‐assembly strategy which synergistically assembles energetic moieties and reduction units. Through this approach, two 2D energetic metal–organic frameworks (EMOFs), {Zn 2 (datz) 2 (CBH) 2 ·H 2 O} n 1 and {Cd(Hdatz) 2 (CBH) 2 } n 2 (Hdatz = 3,5‐diamino‐1,2,4‐triazole, CBH = cyanoborohydride), were successfully synthesized. Compared with pure AP, 5 wt.% of 1 into AP (5% ‐1‐ AP) lowered the decomposition temperature by 116°C, and reduced the apparent activation energy ( E a ) to 84.5 kJ·mol −1 , thereby enabling highly efficient low‐barrier catalysis. Notably, the catalyst induces a dramatic “energy concentration” effect, narrowing the decomposition peak width to 1/14 of pristine AP while the total heat release ( Q ) reaches 1.75 times that of pure AP. TG‐FTIR analysis reveals intensified high‐valent nitrogen oxide signals via enhanced NH 3 oxidation. Theoretical calculations demonstrate that 1 binds more strongly to AP and NH 3 with a lower average surface potential ( V avg ) and greater polarization than 2 , confirming the synergy between electron‐donating CBH − and in situ ZnO in driving efficient electron transfer and concentrated energy release. This EMOFs design demonstrates considerable potential for high‐performance catalytic applications and the development of next‐generation solid propellants.