Microwave-Assisted Synthesis of the Flexible Iron-based MIL-88B Metal–Organic Framework for Advanced Energetic Systems

• Published in: Journal of inorganic and organometallic polymers and materials 2022-07, Vol.32 (7), p.2538-2556
• Main Authors: Zorainy, Mahmoud Y., Kaliaguine, Serge, Gobara, Mohamed, Elbasuney, Sherif, Boffito, Daria C.
• Format: Article
• Language: English
• Subjects: Ammonium perchlorates; Benzene; Chemistry; Chemistry and Materials Science; Decomposition; Dicarboxylic acids; Enthalpy; Ferric oxide; Inorganic Chemistry; Iron; Metal-organic frameworks; Organic Chemistry; Oxidizing agents; Oxygen; Polymer Sciences; Thermal stability; Thermodynamic properties
• ISSN: 1574-1443; 1574-1451
• DOI: 10.1007/s10904-022-02353-6

The 3D metal–organic framework (MOF), MIL-88B, built from the trivalent metal ions and the ditopic 1,4-Benzene dicarboxylic acid linker (H 2 BDC), distinguishes itself from the other MOFs for its flexibility and high thermal stability. MIL-88B was synthesized by a rapid microwave-assisted solvothermal method at high power (850 W). The iron-based MIL-88B [Fe 3 .O.Cl.(O 2 C–C 6 H 4 –CO 2 ) 3 ] exposed oxygen and iron content of 29% and 24%, respectively, which offers unique properties as an oxygen-rich catalyst for energetic systems. Upon dispersion in an organic solvent and integration into ammonium perchlorate (AP) (the universal oxidizer for energetic systems), the dispersion of the MOF particles into the AP energetic matrix was uniform (investigated via elemental mapping using an EDX detector). Therefore, MIL-88B(Fe) could probe AP decomposition with the exclusive formation of mono-dispersed Fe 2 O 3 nanocatalyst during the AP decomposition. The evolved nanocatalyst can offer superior combustion characteristics. XRD pattern for the MIL-88B(Fe) framework TGA residuals confirmed the formation of α-Fe 2 O 3 nanocatalyst as a final product. The catalytic efficiency of MIL-88B(Fe) on AP thermal behavior was assessed via DSC and TGA. AP solely demonstrated a decomposition enthalpy of 733 J g −1 , while AP/MIL-88B(Fe) showed a 66% higher decomposition enthalpy of 1218 J g −1 ; the main exothermic decomposition temperature was decreased by 71 °C. Besides, MIL-88B(Fe) resulted in a decrease in AP decomposition activation energy by 23% and 25% using Kissinger and Kissinger–Akahira–Sunose (KAS) models, respectively.