Two novel heterobimetallic metal-organic frameworks for the enhanced catalytic thermolysis and laser ignition of CL-20

Abstract

The study of multiple complex catalytic mechanisms is currently one of the great scientific issues for the application of high-energy solid propellants. Two novel heterobimetallic metal-organic frameworks (MOFs), Ba4Pb4(CH3CO2)8 [(CH6CO2)4Pb](CH3CO2)4 (PbBa-MOF) and Ba2Ni(CO2H)6(OH2)4 (NiBa-MOF), were prepared via the solvothermal method, and their structures and composition were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) techniques and N2 adsorption/desorption experiment. The thermal decomposition characteristics of the two MOFs and their catalytic performances on the hexanitro hexaazaisowurtzitane (CL-20) thermolysis were also studied by differential scanning calorimetr (DSC) and thermogravimetric-fourier transform infrared spectroscopy-mass spectrum (TG-FTIR-MS) methods. The results showed that the NiBa-MOF presented a lower initial decomposition temperature than the PbBa-MOF, and the difference of the MOFs structures affected the starting point of thermal decomposition. Compared with the pure CL-20, the thermolysis peak temperature and apparent activation energy (Ea) of the CL-20/PbBa-MOF mixture were decreased by 2.2 °C and 23.76 kJ‧mol−1, respectively. The Ea of CL-20/NiBa-MOF mixture was lower and 42.01 kJ‧mol−1, indicating the better catalytic activity of NiBa-MOF. The thermolysis catalytic mechanisms were studied by analyzing the transformation of gas products during the pyrolysis of mixtures. The effect of these two MOFs on the CL-20 thermolysis is primarily owing to the strong attraction of metal cations to electronics, bimetallic synergistic catalysis, and the release of active free radicals. Furthermore, the laser ignition and flame propagation features showed that these two MOFs reduced the minimum ignition power density and ignition delay time of the CL-20, and the flame becomes brighter and more luminous. The influence of the two MOFs on the flame bright spot of CL-20 based mixtures was described.