【作者】 李敏；

【导师】 杨奇；

【作者基本信息】 西北大学 ， 无机化学， 2023， 硕士

【摘要】 近年来,研究人员常将碳纳米材料与含能配合物两者进行复合来研究其对高氯酸铵（Ammonium perchlorate,AP）热分解性能的影响,取得了较为显著的成果。然而,得到的复合材料往往存在复合不均匀、易团聚等不足。为解决此问题,本论文采用原位生长策略得到碳纳米材料@含能配合物,以增强其对AP热分解性能的影响。论文以三（5-氨基四唑）三嗪（H₃TATT）作为富氮能量配体,选取Ag、Pb、Fe为金属离子,采用水热法制备了3例未见文献报道的含能配合物（分别命名为EC-Ag、EC-Pb、EC-Fe）,对其进行了表征并研究了对AP的催化性能。同时,选取本课题组前期制备的催化效果较好的5例含能配合物:Cu（HTATT）（H₂O）₂、[Cu₃（TATT）₂（H₂O）₂]_n、[Pb Zn（TATT）（OH）（H₂O）]_n、{[Mn₄（HTATT）₂（O）₂（H₂O）₂]·H₂O}_n、[Ni（HTATT）]_n（分别命名为EC-Cu1、EC-Cu2、EC-Zn-Pb、EC-Mn、EC-Ni）,采用原位生长策略将上述8例含能配合物分别与氧化石墨烯（GO）、MXene（Ti₃C₂T_x）、碳气凝胶（CA）等碳纳米材料进行复合,得到了24例碳纳米材料@含能配合物,同时采用溶剂-非溶剂法将它们与AP充分混合,研究其对AP热分解性能的影响。主要研究内容如下:（1）以三（5-氨基四唑）三嗪（H₃TATT）为富氮能量配体,选取Ag、Pb、Fe为金属离子,采用水热法制备了EC-Ag、EC-Pb、EC-Fe等3例未见文献报道的含能配合物。使用X-射线粉末衍射仪（XRD）、红外光谱仪（IR）、扫描电子显微镜（SEM）对样品的结构、形貌进行了表征。通过差示扫描量热仪（DSC）及热重分析仪（TG）研究了上述3例含能配合物的热分解行为及其对AP热分解催化性能的影响。研究结果表明,3种含能配合物均可高效催化AP（质量比为1:3）的热分解,其中EC-Fe的催化效果最好,可将AP的分解峰温提前至302.4℃,放热量提升至3290J/g。（2）选取氧化石墨烯（GO）、MXene（Ti₃C₂T_x）及碳气凝胶（CA）作为碳纳米材料,并通过XRD、SEM对其形貌进行了表征。采用原位生长策略,使8例含能配合物分别在3种碳材料表面生长,得到了3大类（GO@含能配合物、MXene@含能配合物、CA@含能配合物）24种碳纳米材料@含能配合物复合材料。采用SEM、XRD、DSC、XPS等方法对这些复合材料进行了表征,同时采用溶剂-非溶剂法将复合材料与AP按照质量比1:3进行混合,利用DSC手段研究了它们对AP热分解催化性能的影响。研究结果表明,24种复合材料均可在含能配合物的基础上进一步提升其对AP热分解的催化效果,这表明碳纳米材料与含能配合物的复合所产生的协同催化作用更有利于AP的热分解。综合分解峰温以及放热量两方面因素,GO@EC-Cu2与CA@EC-Fe具有较好的催化作用,其中GO@EC-Cu2可将AP的高温分解峰温提前88℃,放热量提升至4879 J/g（为纯AP放热量的近11倍）;CA@EC-Fe可将AP的高温分解峰温提前至324.4℃（较纯AP的高温分解峰温提前了90℃）,将低温分解峰温提前至275.1℃,放热量为2835 J/g。这主要是由于含能配合物本身能量较高,且铜离子和铁离子的催化活性高。更多还原

【Abstract】 In recent years,carbon nanomaterials are frequently combined with energetic complexes by researches to investigate their effect on the thermal decomposition performance of Ammonium perchlorate（Ammonium perchlorate,AP）,and remarkable results have been achieved.However,the composite materials obtained often have some shortcomings such as uneven composite and easy agglomeration.To solve this problem,in this paper,carbon nanomaterial@energetic complexes were obtained by in-situ growth strategy to enhance their influence on the thermal decomposition performance of AP.Three energetic complexes（named EC-Ag,EC-Pb,and EC-Fe）that have not been reported in the literature were prepared by hydrothermal method with 3（5-amino tetrazolium）-triazine（H₃TATT）as nitrogen-rich energy ligands,and Ag,Pb,and Fe as metal ions.Their structures were described,and research was done on their catalytic abilities for AP.At the same time,our study team’s 5 best examples of energetic complexes with good catalytic effect were chosen:Cu（HTATT）（H₂O）₂、[Cu₃（TATT）₂（H₂O）₂]_n、[Pb Zn（TATT）（OH）（H₂O）]_n、{[Mn₄（HTATT）₂（O）₂（H₂O）₂]·H₂O}_n、[Ni（HTATT）]_n.The complexes were termed EC-Cu1,EC-Cu2,EC-Zn-Pb,EC-Mn,and EC-Ni,respectively.And these above 8 energetic complexes were synthesized with Graphene Oxide（GO）,MXene（Ti₃C₂T_x）,Carbon Aerogel（CA）and other carbon nanomaterials by an in-situ growth strategy.To explore their effects on AP’s thermal degradation ability,24 carbon nanomaterial@energetic complexes were produced and combined with it using a solvent-non-solvent approach.The following are the primary research findings:（1）Using 3（5-amino tetrazolium）triazine（H₃TATT）as a nitrogen-rich energy ligand and Ag,Pb,and Fe as metal ions,three energetic complexes,including EC-Ag,EC-Pb,and EC-Fe,were created by hydrothermal technique.By using XRD,IR,and SEM,the shape and structure of the samples were determined.Differential scanning calorimetry（DSC）and thermogravimetry（TG）were used to examine the thermal decomposition behavior of the three energetic complexes and their influence on the catalytic performance of AP thermal breakdown.The findings demonstrated that the best catalytic effect on the thermal decomposition of AP occurred when the mass ratio of energetic complex to AP was 1:3 of the three energetic complexes Fe had the best catalytic effect on AP and could raise the peak temperature of AP decomposition to 302.4℃ and the heat release to 3290 J/g.（2）Graphene oxide（GO）,MXene（Ti₃C₂T_x）,and Carbon aerogel（CA）were selected and their morphologies were characterized by XRD and SEM.In situ growth strategy was used to grow 8 cases of energetic complexes on the surface of 3 kinds of carbon nanomaterials respectively,and 24 kinds of carbon nanomaterials@energetic complex composites of 3categories（Go@energetic complex,Mxene@energetic complex,CA@energetic complex）were obtained.24 cases of composite particles were characterized by SEM,XRD,DSC,XPS and other methods.Meanwhile,the composite particles containing 4%,6%,8%,and 10%carbon nanomaterials were characterized by a solvent non-solvent method.The ratio of 1:3was mixed with AP,and their influence on the catalytic performance of AP thermal decomposition was studied by DSC.The results showed that all 24 composite particles had a good catalytic effect on the thermal decomposition of AP,and the overall catalytic effect was better than that of the single energetic complex,indicating that the synergistic effect of carbon nanomaterials and the energetic complex was more conducive to the catalytic thermal decomposition of AP.Considering the factors of decomposition peak and heat release,GO@EC-Cu2 and CA@EC-Fe have a good catalytic effect.GO@EC-Cu2 can transform the original two exothermic peaks of AP into two adjacent exothermic peaks,the high-temperature decomposition peak temperature is advanced 88℃,and the heat release is as high as 4879 J/g（nearly 11 times of the pure AP）.CA@EC-Fe can advance the peak temperature of high-temperature decomposition of AP to 324.4℃（90℃earlier than that of pure AP）,and the peak temperature of low-temperature decomposition by 275.1℃.This is mainly due to the high energy of energetic complex and the high catalytic activity of copper and iron ions.更多还原