卟啉共价修饰的石墨烯杂化材料的制备、表征及性能研究

发布时间：2018-02-10 15:52

本文关键词： 石墨烯卟啉共价修饰杂化材料　出处：《东南大学》2015年硕士论文　论文类型：学位论文

【摘要】：2004年,A. K. Geimand和K. S. Novoselvo利用机械剥离法,首次成功制备出了石墨烯,在之后的10年里,这种二维的碳材料在全球引起了广泛的研究热潮。它具有非常优异的物理化学性质,是导热性最好的、电子传递速度最快和最坚硬的材料。但是,石墨烯的溶剂分散性很差,使其大规模制备加工及应用受到限制。研究者希望利用改性的方法来提高其溶剂分散性和可加工性,而化学功能化是其中最为有效的方法。通过在石墨烯分子上引入功能分子,能够得到综合石墨烯和功能分子优异性能的多功能复合材料。卟啉被称之为“生命的色素”,广泛存在于自然界的生命体内,如动物血液中的血红素就是一种铁卟啉,而绿色植物叶绿体中叶绿素就是一种镁卟啉化合物。卟啉是由四个吡咯环通过次甲基连接形成的大π共轭体系,具有芳香性,是平面的刚性分子。石墨烯/卟啉复合材料具有电子给受体结构,在复合材料中,卟啉与石墨烯分子间能够发生快速的电子转移及能量传递,这使得复合材料具有非常优异的光电化学性质,在非线性光学、光催化、传感等领域具有广泛的应用价。因此,我们希望通过简单的方法合成石墨烯/卟啉复合材料,并研究其光电化学性能,探索其应用价值。而卟啉功能化石墨烯的方法主要有两种,一种是利用π-π作用及静电作用的非共价键结合方式,另一种是利用酯键、酰胺键及碳-碳键的共价键结合方式。前者由于其稳定性较差,因此我们选择共价结合的方式制备石墨烯/卟啉复合材料。具体工作如下：(1)设计并制备了两种轴向共价连接的锡卟啉/石墨烯复合材料,即只在石墨烯边缘引入卟啉的GO'SnP和在石墨烯分子边缘和面内同时引入卟啉的GOSnP。并对它们进行光谱、热重及电镜表征,发现GOSnP与GO'SnP具有不同的形貌,并探究了形貌的形成机理及简单的控制方法。比较GOSnP及GO'SnP的光限幅特性及光电流响应特性,并探究了形貌对于它们电化学性质的影响。(2)设计并制备了非轴向共价连接的氨基卟啉/石墨烯复合材料,只在边缘引入卟啉的GO'TAPP及在边缘和面内同时引入卟啉的GOTAPP。对其进行光谱、热重、电镜表征,并以亚甲基蓝为目标物,研究了它们的光催化降解性能。(3)设计并合成了具有电子“受体-给体-受体”结构的石墨烯/卟啉/富勒烯复合材料GOTAPP-C60,对其进行了光谱、电镜及热重表征,并比较了它与GOATPP的光催化降解亚甲基蓝的能力。
[Abstract]:In 2004, graphene was successfully prepared by mechanical stripping method. In the following 10 years, this two-dimensional carbon material caused a worldwide research boom. It has excellent physical and chemical properties. The materials with the best thermal conductivity, the fastest electron transfer rate and the hardest. However, the solvent dispersion of graphene is very poor. Researchers hope to use modified methods to improve the dispersion and processability of solvents, among which chemical functionalization is the most effective one by introducing functional molecules into graphene molecules. Porphyrin is known as "the pigment of life" and widely exists in the living body of nature, such as heme in animal blood is a kind of iron porphyrin. In green plant chloroplasts, chlorophyll is a magnesium porphyrin compound. Porphyrin is a large 蟺 conjugate system formed by four pyrrole rings connected by methylene. Graphene / porphyrin composite has the structure of electron donor receptor, in which the electron transfer and energy transfer can occur between porphyrin and graphene molecules. As a result, the composites have excellent photochemical properties and are widely used in nonlinear optics, photocatalysis, sensing and so on. Therefore, we hope to synthesize graphene / porphyrin composites by a simple method. The photoelectrochemical properties of porphyrin functionalized graphene were studied and its application value was explored. There are two main methods of porphyrin functionalized graphene, one is the non-covalent bonding mode by 蟺-蟺 interaction and electrostatic action, the other is the use of ester bond. The covalent bonding of amide bond and carbon-carbon bond. Therefore, we choose covalent bonding method to prepare graphene / porphyrin composites. The specific work is as follows: 1) two kinds of axially covalently bonded tin porphyrin / graphene composites have been designed and prepared. In other words, only porphyrin GO'SnP was introduced at the edge of graphene and GOSnP at the same time on the edge and in plane of graphene was introduced. The spectra, thermogravimetric and electron microscopy analysis showed that GOSnP and GO'SnP had different morphologies. The formation mechanism of morphology and the simple control method are discussed. The optical limiting characteristics and photocurrent response characteristics of GOSnP and GO'SnP are compared. The influence of morphology on their electrochemical properties was investigated. The non-axially covalently bonded amino-porphyrin / graphene composites were designed and fabricated. Porphyrin GO'TAPP was introduced only at the edge and the porphyrin GOTAP was introduced simultaneously in the edge and in the plane. The spectra, thermogravimetry and electron microscope were used to characterize the porphyrin, and methylene blue was used as the target material. Their photocatalytic degradation properties were studied. The graphene / porphyrin / fullerene composite GOTAPP-C60 with the structure of electron receptor-donor-receptor was designed and synthesized. It was characterized by spectra, electron microscopy and thermogravimetry. The photocatalytic degradation of methylene blue was compared with that of GOATPP.
【学位授予单位】：东南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ127.11

【相似文献】