Enhanced thermal decomposition performance of sodium perchlorate by molecular assembly strategy

NaClO₄-based molecular perovskite (H₂dabco)[Na(ClO₄)₃] combined with the inorganic oxidizer and organic fuel was prepared by molecular assembly strategy. The high-yield samples were obtained by the one-pot reaction of NaClO₄, HClO₄, and triethylenediamine (dabco). The thermal analysis results showed molecular perovskite (H₂dabco)[Na(ClO₄)₃] with ABX₃-type closely ternary molecular stacking structure had a lower decomposition temperature (381.7 °C) and a higher heat release (2770 J/g) than NaClO₄ (569.2 °C and 353 J/g). The apparent activation energy of thermal decomposition process was reduced by 25 kJ/mol from 184.8 kJ/mol of NaClO₄ to 159.8 kJ/mol of (H₂dabco)[Na(ClO₄)₃]. A synergistic catalysis thermal decomposition mechanism was proposed. The H₂dabco²⁺ from the unique ternary molecular perovskite structure can be favorable for proton excitation under thermal stimuli, and promote the formation of HClO₄ and superoxide radical anions ·O₂ ⁻ further, resulted in the redox thermal decomposition reaction between oxidizer ClO₄ ⁻ and fuel dabco more completely.