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Organic fuels are the main factors affecting the morphology, pore structure and catalytic active sites of metal oxides in solution combustion synthesis (SCS). However, due to the diversity of organic fuel structures, the specific role of organic fuel types on SCS is questionable. In this work, we compared the effects of five organic fuels on the thermocatalytic active sites of graded porous MgCo 2 O 4 nanomaterials. MgCo 2 O 4 (CA-MCO) prepared with citric acid as fuel has the largest specific surface area and the richest pore structure with the largest number of active sites. And the porous CA-MCO exhibited the best catalytic properties that the T HTD of AP decreased by 206.06 °C, the activation energy (E a) decreased by 104.58 kJ·mol−1, and the reaction rate (k) increased by 2.49 s−1. A possible catalytic mechanism for the thermal decomposition of AP was also proposed based on TG-MS and Hall effect tests. Finally, CA-MCO was applied to AP/HTPB-based composite solid propellants (CSPs), and the results showed that the introduction of CA-MCO significantly shortened the ignition delay time of the CSPs (From 29 ms to 8 ms), indicating its potential application in the CSPs. [Display omitted] [ABSTRACT FROM AUTHOR]