无溶剂的能量Ag(Ⅰ)-MOFs的制备及爆炸与安全性能

Preparation,Detonation and Safety Performance of the Solvent-Free Energetic Ag(Ⅰ)-MOFs

基于含能配体3,5?二硝基?1?氢?1,2,4?三唑(2?Hntz)和3,4?双(1?氢?5?四唑基)?氧化呋咱(H_2BTOF),水热条件下制备了两例无溶剂的能量Ag(Ⅰ)?MOFs,[Ag_2(2?ntz)_2]_n(1)和[Ag_2(BTOF)]_n(2)。单晶衍射分析表明,Ag^+中心均为三配位,化合物1为由2?ntz^-采取μ_3?1,2,4模式桥联金属形成的三维框架结构(ρ_1=2.805 g·cm^(-3)),化合物2是由BTOF^(2-)通过五齿桥连?螯合模式连接金属形成的二维折叠层状结构(ρ_2=3.101 g·cm^(-3))。综合热分析(TG?DSC)测试表明,化合物1和2均具有较高的热稳定性,在240℃以前保持框架稳定。以氧弹热量计测定了化合物1和2的恒容燃烧热并计算得到标准摩尔生成焓分别为(1375.74±1.27)k J·mol^(-1)和(1647.42±1.46)k J·mol^(-1)。爆轰和安全性能分析表明,化合物1和2的爆热、爆速和爆压值分别为5.55 k J·g^(-1)和3.78 k J·g^(-1),8.97 km·s^(-1)和7.69 km·s^(-1),44.87 GPa和34.37 GPa,对撞击和摩擦不敏感,属潜在的高能钝感材料。

Based on energetic ligands 3,5-dinitro-1-H-1,2,4-triazole and 3,4-bis(1H-5-tetrazolyl)furoxan,two solvent-free energetic Ag(Ⅰ)-MOFs,[Ag2(2-ntz)2]n(1)and[Ag2(BTOF)]n(2)have been prepared under hydrothermal conditions.Single-crystal X-ray analysis reveals that the Ag+centersin both Ag(Ⅰ)-MOFs are three-coordinated.Compound 1 features a 3D framework(ρ1=2.805 g·cm^-3)constructed by 2-ntz-ligands bridging metal ions with aμ3-1,2,4 mode.Compound 2 presents a 2D folded layer structure(ρ2=3.101 g·cm^-3)formed by BTOF2-ligands linking metal ions with aquinquedentatechelating-bridging coordinationmode.TG-DSC curves demonstrate that both compounds 1 and 2 keep stable until 240℃,exhibiting high thermal stability.The heats of combustion of 1 and 2 are determined by oxygen-bomb calorimeter,and the corresponding standard molar enthalpies of formationare determined to be(1375.74±1.27)kJ·mol^-1 and(1647.42±1.46)kJ·mol^-1,respectively.The detonation and safety performance analyses show that the heat of detonation,detonation velocityand detonationpressureof compounds1 and 2 are,respectively calculated as 5.55 kJ·g^-1 and 3.78 kJ·g^-1,8.97 km·s^-1 and 7.69 km·s^-1,as well as 44.87 GPa and 34.37 GPa.Both compounds 1 and 2 are insensitive to impact and friction,and are good high energy yet low sensitivity materials.