One-pot synthesis of green energetic coordination compounds as high-efficiency combustion catalysts for ammonium perchlorate

Enhancing the combustion performance of ammonium perchlorate (AP) remains a critical challenge in developing high-performance solid propellants. To achieve efficient and safe combustion regulation, energetic coordination compounds (ECCs) offer a promising solution by virtue of their catalytic activity, intrinsic energy release, and reduced environmental impact. In this work, a series of N,N-bis(1H-tetrazol-5-yl)amine (BTA)-based ECCs was synthesized through a simple, green, and efficient one-pot method. Six new ECCs were successfully obtained: [Fe(BTA)₃](HGua)₃·3H₂O (ECC-1), [Fe(HBTA)₃](HGua)(H₂BTA)·5H₂O (ECC-2), [Mn(BTA)₃](HGua)₄·3H₂O (ECC-3), [Al(BTA)₃](HGua)₃·4H₂O (ECC-4), [Co(HBTA)(BTA)₂](HGua)₃·4H₂O (ECC-5), and [Ni(BTA)₃](HGua)₄·6H₂O (ECC-6). These ECCs were comprehensively characterized to evaluate their energetic properties, thermal stability, mechanical sensitivities, and catalytic effects on AP decomposition. Thermal analysis indicates that most BTA-based ECCs significantly accelerate AP decomposition, lowering its high-temperature decomposition peak by up to 81 °C Moreover, these complexes exhibit good thermal stability with decomposition temperatures ranging from 141 °C to 312 °C, low mechanical sensitivity with impact sensitivities above 40 J (except for ECC-2 at 5 J), and high energy output arising from the nitrogen-rich BTA ligand. Electrothermal ignition experiments further demonstrate their capability to promote and stabilize the combustion of HMX/AP composites, yielding accelerated burning rates and enhanced flame propagation, which highlights their substantial potential as green and efficient combustion catalysts for next-generation solid propellants.