【作者】 张加涛；

【导师】 李亚栋；

【作者基本信息】 清华大学 ， 化学， 2006， 博士

【摘要】 铜族金属及金属氧化物纳米材料因其独特的物理化学性质,在光学、催化、气敏、磁学等领域有着广泛的应用。基于纳米材料的形貌控制合成,深入研究形貌、微观结构对表面性能的影响,对指导纳米材料的性能开发和应用具有重要意义。本论文旨在探索金属Ag、Au纳米晶的调控合成及其形貌和暴露晶面对表面等离子体共振拉曼散射（SERS）效应增强的影响和应用,探讨铜的氧化物纳米晶的调控合成及形貌对其气敏、磁性、催化等性能的影响。利用溶剂热或液相回流法调控合成出纳米线、纳米立方块、不同剪切度的三角片等不同形貌的Ag纳米晶,通过对上述不同形貌银纳米晶的SERS增强检测,发现Ag纳米晶由于晶面暴露不同,SERS活性有明显的差异。因此提出了活性晶面的概念,为进一步提高金属纳米颗粒的SERS增强提供了新思路。基于活性晶面对SERS增强的影响,制备了高暴露活性晶面的纳米Ag、Au颗粒,得到了高SERS活性的金属基底。并将其负载在普通光纤或光子晶体光纤上,成功的实现了SERS信号的传输,为SERS在探针分析检测方面的应用奠定了基础。采用液相回流法合成了准单分散的氧化亚铜纳米球,通过调控反应物浓度、温度等实现了对纳米球尺寸、结晶性和自组装性能的控制。与八面体微米块、纳米立方块等形貌的氧化亚铜材料比较,研究了形貌对氧化亚铜气敏和磁性质的影响。将这一方法推广,也实现了对AgBr亚微米球的调控合成。用所制备的准单分散氧化亚铜纳米球为模板,利用气相氧化或者还原的方法,得到了氧化铜与金属铜的纳米球;利用液相法实现了对氧化亚铜纳米球的核壳结构包覆、转化及金属负载。利用合成的Ag三角片,通过溶剂热一锅法制备了Ag@Cu₂O核壳结构。并研究了上述纳米结构的光学、催化、气敏等性质。更多还原

【Abstract】 Owing to unique physical and chemical properties, copper family metal and metal oxides in nanostructure have exhibited promising applications in catalysis, sensing, optics, and magnetics. With the development of shape-controlled synthesis of inorganic nanomaterials, controlling their surface structures and investigating effects to their surface properties will be significant to direct their applications. In this dissertation, systematic explorations have been carried out on shape controlled synthesis of copper family nanomaterials and the corresponding effect to SERS, SPR, gas sensor, catalysis, and magnetics properties.Using sovolthermal method, the truncation of Ag nanoplates and their SPR properties have been controlled. Based on preparation of silver nanowire, nanoplates, nanoparticles, and nancubes exposed different crystal faces, the crystal face effects to SERS enhancement have been found, which would contribute to SERS mechanism study, especially chemical mechanism. According to the crystal face influence to SERS enhancement, we have prepared Ag, Au nanoparticles with high SERS sensitivities and realized the applications on optical fiber probe detection.A simple solution method has been developed to prepare nearly monodisperse single-crystalline Cu₂O nanospheres. The size, crystallization, and self-assembly of as-prepared Cu₂O nanospheres have been controlled by changing reagent concentration. Compared with the shapes of nanocubes, micro-octahedrons, the shape effects to their gas sensitivities and magnetic performance have been studied. Using this solution method, the AgBr microspheres can be prepared too.Using as-prepared Cu₂O nanospheres, based on gas phase reaction, the CuO and Cu nanospheres have been prepared. The Cu₂O p-n core-shell structures and transformation without shape changing have been achieved inorder to satisfy more applications. Based on Ag, Au loading on the Cu₂O nanospheres, their application on CO catalytic oxidation has been explored. A one-pot method to synthesize Ag@Cu₂O core-shell nanoparticles with interesting optical properties has been established.更多还原