【作者】 马艾丽；

【导师】 许并社；

【作者基本信息】 太原理工大学 ， 材料加工工程， 2007， 硕士

【摘要】 零维碳材料以独特的笼状结构和电学、磁学、力学、化学等特殊的性能而成为高科技材料领域的一颗新星。零维碳材料聚集了全球许多科学家的关注。理论计算和实践研究表明，零维碳材料潜在的应用价值十分巨大。近年来，国际学术杂志上有关零维碳材料的文章数量增加较快，可以说零维碳材料的研究正方兴未艾。迄今为止，国内外对零维碳材料的制备方法和性能进行了广泛的研究，但是对零维碳材料的吸附性能和应用研究尚少。本文采用化学气相沉积法(CVD)分别以乙炔、甲苯以及乙炔和甲苯混合物为原料，探索了制备碳微球的理想工艺参数。采用水下电弧放电法和化学气相沉积法(CVD)制备了单纯和内包金属纳米Fe颗粒两种形貌不同的纳米洋葱状富勒烯。利用X-射线衍射(XRD)、场发射扫描电子显微镜(FESEM)和高分辨透射电子显微镜(HRTEM)对不同工艺方法制备的零维碳材料进行了观察表征和分析。实验证明：在没有催化剂的条件下，以甲苯和乙炔的混合物为碳源，温度为1000℃时能制备出大量高纯度、形貌较好尺寸均匀的碳微球；对理想工艺参数下所得的碳微球分别进行微波等离子体处理和高温真空处理，结果发现经过处理，特别是经过高温真空处理后碳微球的石墨化程度得到提高，内部出现了清晰的石墨化条纹；CVD法制备出了大量的内包金属Fe颗粒的纳米洋葱状富勒烯；水下直流电弧放电法以光谱纯石墨棒为碳源制备了大量的单纯纳米洋葱状富勒烯。对理想条件下得到的不同零维碳材料进行硝酸氧化处理后，发现并没有在其表面引入官能团。为了便于研究，硝酸氧化采用了不同的氧化时间。本文还在液氮温度77K下测定不同工艺方法制备的零维碳材料在硝酸氧化前后的吸附等温线和孔分布曲线。结果表明：碳微球的吸附等温线为混合型，经过石墨化处理之后孔容降低，比表面积增加；经微波等离子体处理后其吸附能力有所增加，而经过高温真空热处理之后吸附能力有所下降；两种富勒烯的吸附等温线类型极为类似，属于比较复杂的混合型吸附等温线类型，单纯纳米洋葱状富勒烯和内包金属Fe的纳米洋葱状富勒烯的吸附性能有一定差异，单纯纳米洋葱状富勒烯的吸附能力较低；由于碳微球颗粒较大，而且又是实心结构，比表面积和孔容都比富勒烯碳洋葱要相差一个数量级；经过硝酸氧化后，零维碳材料的吸附等温线类型由原来的混合型转变为典型的Ⅲ型；碳微球只有经过15h的氧化后吸附量呈现上升，而纳米洋葱状富勒烯的吸附量在氧化后只呈现了下降趋势；碳微球在经过6h、12h和15h的氧化后比表面积有所增加，而纳米洋葱状富勒烯只有在经过12h的氧化后才有所上升。更多还原

【Abstract】 As its unique spherical structure and special properties in electrinics, magnetics, mechanics, chemistry and so on, zero-dimensional carbon materials has been a new star in high-tech materials field. It attracts many worldwide scientists to focus on it. Theory calculation and practical study indicate that zero-dimensional carbon materials has huge potential application value. In recent years, the articles about zero-dimensional carbon materials in the international science journal increase greatly, indicating that the study on zero-dimensional carbon materials is in the ascendant. So far, study on the preparation and properties of zero-dimensional carbon materials have been carried out widely in abroad and at home, but the study on its adsorption capability and application is rather less.In this paper, ideal parameter for preparation of carbon microspheres was probed by chemical vapor deposition (CVD), using acetylene, toluene and mixture of them as carbon source. Individual nano onion-like fullerenes and Fe nanoparticles encapsulating nano onion-like fullerenes (nano-Fe@OLFs) were synthesized by DC arc-discharge in water and CVD. The microstructures of zero-dimensional carbon materials by different methods were characterized and analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The results revealed that without catalyst, a great deal of carbon microspheres with high purity and uniform diameter could be prepared from the mixture of acetylene and toluene at 1000°C; After microwave treatment and high temperature vacuum treatment, on the carbon microspheres prepared with this parameter, the graphite degree was enhanced greatly. Especially after high temperature vacuum treatment clear graphite stripe appeared inner; Great deal of individual nano onion-like fullerenes and Fe nanoparticles encapsulating nano onion-like fullerenes (nano-Fe@OLFs) were synthesized by DC arc-discharge in water and CVD; After nitic acid oxidation on different zero-dimensional carbon materials no function corps were introduced to the surface of them. Different oxidation time was performed on them.Nitrogen adsorption isotherms for all the samples studied are measured at 77K on Sorptomatic 1990 automatic physics and chemistry instrument. The results show that adsorption isotherms of carbon microspheres are complex. Both after high temperature vacuum and microwave treatment the pore volume decreased, and the specific surface area increased. After high temperature vacuum treatment the adsorption capability decreased but after microwave treatment it increased; Two fullerenes had similar complex adsorption isotherm. The adsorption property of this two was different, and the adsorption capability of individual nano onion-like fullerenes was lower; As its big size and solid structure, the adsorption capability of carbon microspheres was far lower than that of fullerenes; After nitric acid oxidation, the adsorption Isotherms of all the samples translated to III type; Only after 15h oxidation the adsorption amount raised, but that of fullerenes dropped consistently; The specific surface area of carbon microspheres increased after 6h, 12h and 15h oxidation, but that of fullerenes increased only after 12h oxidation.更多还原