Fabrication of Low‐Dimensional Nitrogen‐Rich Organic–Inorganic Hybrid Halide Perovskites and Their High Catalytic Efficiency for Thermal Decomposition of Ammonium Perchlorate

ABSTRACT Organic–inorganic hybrid halide perovskites show remarkable catalytic activity in photoelectrocatalysis; their application in promoting the thermal decomposition of ammonium perchlorate (AP) remains largely unexplored, however. In this study, with the incorporation of high‐enthalpy nitrogen‐rich azolium cations into A‐sites, six novel low‐dimensional ABi 2 I 8 ‐type halides 1–6 were synthesized. For the first time, their catalytic performance for AP pyrolysis was explored. The results indicated that the addition of 5 wt.% 1–6 to AP exhibited excellent catalytic performance, with 1 demonstrating the most effective catalysis. 1 shifted the high‐temperature decomposition (HTD) peak of AP from 414.6°C ± 0.50°C to 271.6°C ± 0.44°C, increased its heat release from 774±15.0 J g −1 to 1962±21.0 J g −1 , and reduced the HTD activation energy of AP. The effective catalytic behavior of 1 is attributed to the introduction of nitrogen‐rich 1,2,4‐triazolium cation at its A‐site and its 1D structure. Electrochemical and TG‐FTIR‐MS analysis revealed the AP thermal decomposition mechanism. DFT calculations showed that the in situ formed active β‐Bi 2 O 3 nanoparticles during pyrolysis are beneficial to NH 3 adsorption and NO x formation. This study elucidates the structure‐activity relationship of high‐nitrogen halide perovskites in the catalytic thermal decomposition of AP, offering new insights for the development of efficient AP combustion catalysts.