In the present study, the effect of four nanocatalysts, namely, purified multi‐walled carbon nanotubes (MWCNTs), MWCNTs functionalized with ionic liquid (MWCNTs‐IL), MWCNTs decorated with iron nanoparticles (Fe‐MWCNTs) and the hybrid Fe‐MWCNTs‐IL on the thermal decomposition of ammonium perchlorate (AP) is highlighted. Firstly, MWCNTs are purified and impregnated under infrared irradiation followed by calcinations to obtain Fe‐MWCNTs. Secondly, a green ionic liquid (IL), based on choline chloride and urea is synthesized and used for the functionalization of MWCNTs and Fe‐MWCNTs to obtain MWCNTs‐IL and Fe‐MWCNTs‐IL, respectively. Subsequently, these nanomaterials at a ratio of 1 wt.% are introduced to AP to assess their catalytic effect using DSC and TG analyses. The obtained results highlight the catalytic effect of the functionalized MWCNTs on the thermal decomposition of AP for which a decrease in decomposition temperature of 10.7, 48.4 and 49.9 °C with an increase in decomposition enthalpy of 56.76, 689.99 and 861.11 J/g for AP supplemented with MWCNTs‐IL, Fe‐MWCNTs and Fe‐MWCNTs‐IL, respectively. Furthermore, the calculation of the kinetic parameters confirms that the best catalytic effect is obtained with the Fe‐MWCNTs‐IL hybrid, revealing the synergistic effect of iron and ionic liquid. This combination allows obtaining the lowest activation energy (∼120 kJ/mol).

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