有机小分子修饰石墨烯材料的制备与性能研究

发布时间：2018-05-09 04:22

本文选题：有机小分子修饰石墨烯 + 多相催化剂　；参考：《西华师范大学》2017年硕士论文

【摘要】：本文系统研究了有机小分子修饰的石墨烯材料在Knoevenagel缩合反应和C N偶联反应中的应用,通过简单的制备方法合成了具有不同性能的石墨烯材料,并采用不同的表征方法对各种石墨烯材料进行了详细分析,主要研究内容如下:首先,通过一锅法制备出了维生素B1修饰氧化石墨烯材料(GO VB_1),并采用原位化学还原的方法合成了铜负载的VB_1修饰氧化石墨烯复合材料(Cu VB_1 G)。利用傅里叶变换红外光谱(FT IR)、X 射线单晶衍射(XRD)、扫描电子显微镜(SEM)、X 射线光电子能谱(XPS)和透射电子显微镜(TEM)等手段对这两种复合材料进行了表征。结果表明,VB_1成功修饰到氧化石墨烯上,铜也成功负载到了GO VB_1材料表面,且主要以零价形式存在。催化实验结果表明,GO VB_1材料作为多相催化剂用于Knoevenagel缩合反应不仅具有很好的催化活性,而且催化剂用量少,易分离循环,循环性能优异。Cu VB_1 G复合材料在碘苯和咪唑的C N偶联反应中,催化活性表现一般。这可能是由于VB_1上的S元素制约了Cu VB_1 G材料的活性。其次,我们也通过一锅法制备了氨基酸修饰氧化石墨烯材料(A GO),并对所有材料进行了详细的表征。结果表明,A GO作为多相催化剂催化Knoevenagel缩合反应具有反应时间短,反应条件温和和所用溶剂绿色无害等优点。此外,本文还系统研究了L 精氨酸修饰的氧化石墨烯催化剂(Arg GO)在Knoevenagel缩合反应中的通用性和循环稳定性。最后,我们还通过简单的化学方法合成了1,3 二氨基石墨烯(NH_2 G NH_2)材料,并对其进行了详细的表征。结果表明,1,3 二氨基官能团成功修饰到石墨烯表面,并且可通过配位作用固载CuI。NH_2 G NH_2材料可用作多相配体,促进Cu I催化C N偶联反应,获得良好的收率。这个反应体系相较于之前的报道,反应温度更低。此外,这种方法可以轻松实现产物的纯化和催化剂的分离。
[Abstract]:In this paper, the applications of graphene modified with small organic molecules in Knoevenagel condensation and C-N coupling reactions were systematically studied. Graphene materials with different properties were synthesized by a simple preparation method. Various graphene materials are analyzed in detail by different characterization methods. The main contents are as follows: firstly, The vitamin B1 modified graphene oxide material go VB1 was prepared by one pot method. The copper-supported VB_1 modified graphene oxide composite was synthesized by in situ chemical reduction method. The composites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray single crystal diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPSS) and transmission electron microscopy (TEM). The results showed that VB-1 was successfully modified onto graphene oxide, and copper was loaded on the surface of go VB_1, which mainly existed in the form of zero valence. The results of catalytic experiments show that the VB_1 material used as multiphase catalyst not only has good catalytic activity for Knoevenagel condensation reaction, but also has less amount of catalyst and is easy to separate and recycle. The catalytic activity of VB_1 G composite with excellent cycling performance was general in the C-N coupling reaction of imidazole and iodized benzene. This may be due to the fact that the activity of Cu VB_1 G is restricted by S element on VB_1. Secondly, Amino acid modified graphene oxide was prepared by one pot method, and all the materials were characterized in detail. The results show that the reaction of Knoevenagel condensation catalyzed by Apogo as a heterogeneous catalyst has the advantages of short reaction time, mild reaction conditions and harmless solvent. In addition, the generality and cyclic stability of L-arginine modified graphene oxide catalyst (Arg) in Knoevenagel condensation reaction were systematically studied. Finally, we have synthesized and characterized the 1 ~ (3) diaminodiaminoglyphene (SGP) -NH _ 2 / G _ (NH _ 2) _ 2 material by a simple chemical method. The results showed that the functional group was successfully modified to the surface of graphene, and the CuI.NH_2 G + NH_2 material could be used as a multiphase ligand to promote the C ~ (2 +) -N coupling reaction catalyzed by Cu I, and a good yield was obtained. The reaction temperature is lower than previously reported. In addition, this method can easily achieve the purification of products and the separation of catalysts.
【学位授予单位】：西华师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TB332

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