铜钯功能化石墨烯材料的制备及其催化偶联反应的研究

发布时间：2018-04-03 18:47

本文选题：石墨烯　切入点：催化　出处：《济南大学》2017年硕士论文

【摘要】：作为21世纪的新型材料,石墨烯是由碳原子以sp2杂化连接的单原子层构成的新型二维原子晶体,它具有优异的电学,力学,热学,光学性能和大的比表面积,这使得石墨烯成为理想的金属纳米材料的负载体,在高新技术领域,如:光电转换应用、能源催化应用、生物医学应用等方面展现出巨大的应用前景。本论文通过对石墨烯材料的研究,进行了功能化石墨烯材料的探索的研究,对石墨烯为载体的催化反应进行了深入研究。在本论文中,我们合成了一系列铜钯功能化的石墨烯材料并将其运用到卤代烃的Suzuki偶联反应之中,并利用高效液相色谱和气相色谱对其催化活性进行了评价,结果证明具有优越的效率和选择性。主要研究内容和成果如下:(1)我们通过对Hummers方法的改进,选用了两种途径来制备氧化石墨烯(GO),并通过对形貌的表征,选取了合适的制备途径,制备了在水溶剂中具有很好分散性和低晶格缺陷的温和氧化的氧化石墨烯;(2)我们对铜钯功能化石墨烯的制备路线进行了探索,选用了以碱性条件下的水合肼作为还原剂和乙二醇作为溶剂的溶剂热还原法两种方法为制备路径,实验证明我们选用乙二醇作为溶剂的溶剂热法为制备方法,制备出了具有高效催化活性且粒子附着较为均匀和密集的石墨烯材料。(3)我们对不同钯铜比例的石墨烯材料的催化效率进行了分析,并且对实验条件进行了探索,最终,确定了最佳效率的催化材料为铜钯比例为1:1的功能化石墨烯材料,最佳的实验反应温度为80oC,实验的最佳溶剂为乙醇和水比例为1:1。(4)我们对不同的卤代烃进行了Suzuki偶联反应的效率和选择的探讨,我们发现,所制备的铜钯功能化石墨烯具有十分优越的效率和选择性。卤代烃化合物转化率超过90%,联苯化合物选择性达到95%,对多种卤代烃化合物有优秀的催化适用性。(5)对于催化的循环利用效率,我们以溴苯作为模型了探讨,发现铜钯功能化石墨烯这一非均相催化剂有着十分优越的效率和转化率,循环五次后,效率仍能达到90%以上,选择性在95%以上,用TEM进行了形貌特征的检测,发现催化剂仍保持良好的形貌特征和密集的粒子附着。
[Abstract]:As a new material in the 21st century, graphene is a new two-dimensional atomic crystal composed of carbon atoms connected by sp2 hybrid monatomic layer. It has excellent electrical, mechanical, thermal, optical properties and large specific surface area.This makes graphene an ideal negative carrier for metal nanomaterials and has shown great application prospects in high-tech fields such as optoelectronic conversion applications, energy catalytic applications, biomedical applications, and so on.Through the study of graphene materials, the functional graphene materials were studied, and the catalytic reaction of graphene as the carrier was studied.In this thesis, a series of copper-palladium functionalized graphene materials were synthesized and applied to the Suzuki coupling reactions of halogenated hydrocarbons, and their catalytic activity was evaluated by high performance liquid chromatography (HPLC) and gas chromatography (GC).The results show that it has superior efficiency and selectivity.The main research contents and results are as follows: (1) by improving the Hummers method, we have selected two ways to prepare graphene oxide.A mild oxidized graphene oxide with good dispersion and low lattice defects in aqueous solvents was prepared. We have explored the preparation route of copper-palladium functionalized graphene.The solvothermal reduction method with hydrazine hydrate as reducing agent and ethylene glycol as solvent was chosen as the route of preparation. The experiment proved that the solvothermal method with ethylene glycol as solvent was used as the preparation method.The graphene materials with high catalytic activity and uniform and dense particle adhesion were prepared. We analyzed the catalytic efficiency of graphene materials with different palladium and copper ratios, and explored the experimental conditions.The best efficient catalyst is functionalized graphene material with the ratio of copper and palladium 1:1.The optimum reaction temperature is 80oC and the optimum solvent is ethanol / water ratio of 1: 1.0.We have studied the efficiency and selection of Suzuki coupling reaction for different halogenated hydrocarbons.The copper-palladium functionalized graphene has excellent efficiency and selectivity.The conversion of halogenated hydrocarbons exceeds 90, the selectivity of biphenyl compounds reaches 95%, and has excellent catalytic applicability for various halogenated hydrocarbons.It was found that the copper-palladium functionalized graphene was a heterogeneous catalyst with excellent efficiency and conversion. After five cycles, the efficiency was still over 90% and the selectivity was over 95%. The morphologic characteristics of the catalyst were examined by TEM.It was found that the catalyst maintained good morphology and dense particle adhesion.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ127.11;O621.251

【参考文献】