Construction Of A Class Of Triazole-derived Energetic Complexes And Its Catalytic Performance

Recently,triazole-derived energetic complexes have become an important development direction in the field of energetic materials.To improve the detonation properties and stability,we chose triazole derivative as ligand to synthesis complex.We studied the single crystal structure,stability and non-isothermal kinetics of the complexes and explored the application properties of the complexes such as detonation velocity,friction sensitivity,impact sensitivity and catalytic properties of AP.The main research contents of this paper are as follows:(1)By utilizing ligand 3-amino-1,2,4-triazole-5-carboxylic acid(H2atzc),12 nex complexes,namely,[M(Hatzc)a(atzc)b(H2O)c]nH2O(M=Mn?Fe?Co?Ni?Cu?Zn?Cd)?ZnCl(atrz)(atrz=3-amino-1,2,4-triazole)?Ln(Hatzc)(atzc)(H20)(Ln=Ce?Pr?Nd?Gd)have been obtained by solution method,hydrothermal method and solution evaporation method and characterized by IR,elemental analysis and single-crystal X-ray diffraction.(2)B3LYP/6-311G and HF/6-311G level were calculated to analyze the geometric optimization and charge distribution of the ligand.The results demonstrated that N3 on the triazole ring,01 and 02 on the carboxyl group have strong negative charge,which are easy to coordinate.The single crystal structure analysis showed that the ligand exhibited three coordination modes,and the N3 and 01 atoms in the ligand were easily chelate coordination,which is consistent with the above theoretical calculation results.(3)The TG-DTG curve indicates that the complex usually loses crystal water and coordination water,exhibits high thermal stability.And the combustion products are metal oxides or metal elements.(4)Kissinger's method and Ozawa-Doyle's method are employed to determine the apparent activation energy(Ea)and the pre-exponential factor(InA),which indicates that the Ea of the complexes are relatively close,and the reaction rate constant k are obtained by the Arrhenius equation of the energy complexes.(5)The structures of complexes 1-4,6-8 were optimized by density functional theory calculation(DFT),and the explosive heat of the complex was calculated by the explosion equation.The complexes exhibit prominent heats of detonation,higher than TNT,TATB,and RDX.The velocity(D)detonation pressure(P)of the complexes were estimated by the Kamlet-Jacobs equation.Compared with the conventional explosive,the complexes exhibited high detonation pressure.The sensitivity performance of the complex was tested.The results show that the impact and friction sensitivities of the complexes were higher than 40 J,360 N,respectively,classifying them as "insensitive",which can be applied as potential explosives.By comparison,complexes present high detonation properties.(6)To check the effects on thermal decomposition of AP after adding the compound,the Kissinger's method is used to investigate the activation energy(Ea)and pre-exponential factor(A)of thermal decomposition for AP and AP with additives by DSC measurement with four different heat rates.By comparison,the catalytic effect of the transition metal complex are better than that of the rare earth complex.Complexes 3 and 4 exhibit excellent catalytic effects,while rare earth complexes have weaker catalytic effects.