【作者】 李健；

【导师】 叶迎华；

【作者基本信息】 南京理工大学 ， 军事化学与烟火技术， 2012， 硕士

【摘要】 本文采用氢气泡模板法,用硫酸铜和硫酸的混合溶液作为电解液,以副反应中产生的氢气泡为模板,制备得到多孔铜薄膜。采用扫描电镜(SEM)以及激光共聚焦显微镜(LSCM)对多孔铜进行表征,发现多孔铜具有海绵状结构,孔壁由不同尺度的铜微晶构成,这使得多孔铜具有较高的比表面积和孔隙率。重点研究了不同种类和浓度的添加剂对多孔铜三维结构形貌的影响,确定了添加剂的较优添加量,即HCl和PEG较为合适的添加量为10mmol/L和2g/L,十二烷基磺酸钠较为合适的添加量为0.1g/L。将高氯酸铵的丙酮饱和溶液滴加到多孔铜的表面,制备得到多孔铜-NH4ClO4复合材料。运用扫描电镜(SEM)以及X射线衍射仪(XRD)对填充前后的多孔铜形貌对比观察,发现填充后的多孔铜变得更为密实,孔壁上附着的深灰色物质即为NH4ClO4。对多孔铜-NH4ClO4复合材料进行热分析研究,结合TG-DSC-MS-IR联用仪,初步研究了多孔铜与NH4ClO4的反应机理尤其是多孔铜对NH4ClO4的热分解催化机理。使用DSC和XRD研究复合材料的反应过程,初步推断多孔铜-NH4ClO4复合材料在热分解发生如下反应：6NH4ClO4+4Cu→2CuCl+2CuO+3N2↑+12H2O↑+2Cl2←+5O2↑结合电子转移理论以及质子转移理论,可知较大的比表面积以及存在的不饱和状态均对多孔铜的催化性能十分有利。在热分解实际反应过程中,真正起关键催化作用的是多孔铜与NH4ClO4反应生成的CuO,CuO在NH4ClO4低温以及高温热分解的过程中,起到了很重要的桥梁式的催化作用,低价态的氧化物价带,通过接受转移的电子,实现了氧化物价带中空穴的湮没,进而催化了NH4ClO4的热分解。更多还原

【Abstract】 The hydrogen bubble template method was applied, using a mixed solution of copper sulfate and sulfuric acid as the electrolyte. The hydrogen bubbles produced in the side reactions are the template to prepare porous copper film. The SEM and LSCM were applied to characterize the porous copper. It is found that the porous copper has sponge-like structure and the walls are composed of different scales of copper crystallite, which makes the porous copper has a high specific surface area and porosity. This experiment is focused on the impact of different types and concentrations of additives on the morphology of three-dimensional structure of the porous copper to determine the optimum amount of additive. The saturated solution of ammonium perchlorate in acetone was added to the surface of the porous copper to prepare the NH4ClO4and porous copper composite materials. SEM and XRD were applied to characterize the filled porous copper and it is found that the filled porous copper becomes more dense and the dark gray material attached to the walls is NH4ClO4.TG-DSC-MS-IR was employed to conduct the thermal analysis of the porous copper and NH4ClO4composite materials to show the reaction mechanism, especially the catalytic mechanism that the porous copper shows on the thermal decomposition of NH4ClO4. DSC and XRD were applied to consider the reaction process of the composite materials, and the concluded thermal decomposition reactions of the porous copper and NH4ClO4composite materials is as follows:6NH4ClO4+4Cu→2CuCl+2CuO+3N2↑+12H2O↑+2Cl2↑+5O2↑The electron transfer and proton transfer theory are employed to interpret the enhanced catalytic properties of porous copper with a larger specific surface area and unsaturated condition. In the process of thermal decomposition reaction, the key catalytic role is CuO produced by the porous copper and NH4ClO4. In the thermal decomposition process of NH4ClO4, CuO played a very important bridge-type catalytic role, in which the low valence oxide valence band achieves cavity annihilation by accepting the transfer of electronic to promote the thermal decomposition of NH4ClO4.更多还原