石墨烯基联四唑含能配位聚合物的制备、表征及催化活性  

Graphene-templated Energetic 5,5′-Bistetrazole Coordination Polymers and Their Catalytic Effects on Thermal Decomposition of RDX and AP

作　　者：张雪雪 吕杰尧 何伟[1] 陈书文 杨志剑[2] 严启龙 ZHANG Xue-xue;Lü Jie-yao;HE Wei;CHEN Shu-wen;YANG Zhi-jian;YAN Qi-long(Science and Technology on Combustion,Internal Flow and Thermo-structure Laboratory,Northwestern Polytechnical University,Xi′an 710072,China;Institute of Chemical Materials,CAEP,Mianyang 621999,China)

机构地区：[1]西北工业大学燃烧、热结构与内流场重点实验室,陕西西安710072 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2019年第9期749-758,共10页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金面上项目（51776176）;国防科技创新特区项目

摘　　要：采用溶剂热法制备了一系列新型石墨烯基联四唑钝感含能配位聚合物,该含能配位聚合物以钴和镍两种金属离子为典型配位中心,氧化石墨烯(GO)为结晶掺杂物,配体选用1,1′-二羟基-5,5′-联四唑(DHBT)和5,5′-联四唑(H2BT)。通过调节合成工艺参数,成功制备出GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT与β-GO-Ni-BT五种含能催化剂。采用粉末衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)/能谱(EDS)和差热扫描量热仪(DSC)-热重分析仪TG等技术对这五种含能催化剂形貌结构进行了表征,并采用DSC-TG研究了GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT对高氯酸铵(AP)和黑索今(RDX)催化热分解性能的影响。结果表明,石墨烯诱导联四唑配合物结晶可减少晶体缺陷,从而降低热点产生几率,提高热稳定性。其中,GO-Co-DBT、GO-Ni-DBT与GO-Ni-BT分解温度高于200℃。石墨烯基联四唑配合物含能催化剂对AP与RDX的热分解反应具有显著的催化作用,通过转移O元素与NH4^+反应来提高生成NH3和H2O的反应深度,使AP两个放热峰重叠,总放热量增加,催化效应显著。AP的归一化放热量增至2757.0 J·g^-1,转晶对应的吸热峰热值降低至23.2 J·g^-1,RDX的归一化放热量提高至2898.0 J·g^-1,相对于纯AP,RDX放热量提高50%以上,在保证催化效果的同时提高体系的热稳定性。Several novel GO-based bis-tetrazole energetic coordination polymers(ECPs)were designed and prepared by solvothermal method,which contain cobalt(Ⅱ)and nickel(Ⅱ)as coordination center,5,5′-bis-tetrazole(H2BT)and 5,5-bis-tetrazole-1,1-dioldehydrate(DHBT)as ligand. The coordination polymer crystal can be controlled through regulating the experimental conditions. Five typical promising catalysts of GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT and β-GO-Ni-BT were characterized by XRD(X-ray diffraction),XPS(X-ray photoelectron spectroscopy),SEM(scanning electron microscope)/EDS(Energy Dispersive Spectrometer) and DSC(differential scanning calorimetry)-TG(Thermogravimetric Analysis) techniques.DSC-TG results of GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT indicate that GO-based bis-tetrazole energetic coordination polymers could reduce crystal defect,then lower the hot pot and improve thermostability,so the dicomposition temperatures of GO-Co-DBT,GO-Ni-DBT and GO-Ni-BT are all above 200 ℃. These ECPs as energetic catalysts have significant catalytic effect on thermal decomposition of AP and RDX. The reason can be that more O elements being transferred to react with NH4^+ results in increasing the yields of NH3 and H2O,which also made two decomposition peaks of AP overlap and the whole heat release increase. The heat releases of AP and RDX catalyzed by graphene-templated bis-tetrazoles are 2757.0 J·g^-1 and 2898.0 J·g^-1 respectively,which improve more than 50% compared with pure AP and RDX. The endothermic peak of AP corresponding to the crystal transformation is also reduced to 23.2 kJ·mol^-1. Prepared GO-based bis-tetrazole energetic coordination polymers could enhance thermostability and decomposition efficiency of AP and RDX.

关 键 词：石墨烯 含能催化剂 含能配位聚合物 晶型调节 热稳定性 催化机制 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] V512[航空宇航科学与技术—航空宇航推进理论与工程]