氮掺杂介孔碳材料的制备表征及催化的有机合成反应研究

发布时间：2018-03-28 11:57

本文选题：氮掺杂介孔碳　切入点：催化　出处：《南京航空航天大学》2015年硕士论文

【摘要】：有序氮掺杂介孔碳材料是指一类含有氮原子组分的新型介孔碳材料,广泛用于储氢材料、电极材料以及多相加氢催化剂载体等。但是将其用于催化有机合成反应的报道比较少。本文从有序氮掺杂介孔碳材料的制备出发,以新颖的方法制备出含氮量可观、比表面性能良好、孔径分布规则的有序氮掺杂介孔碳材料。然后以该碳材料作为载体,负载纳米铜颗粒作为催化剂在较为温和的条件下实现了端炔的自身和交叉偶联反应以及由此衍生的噻吩、呋喃一锅法分步合成反应。首先,在碳材料的制备过程中,本文以2,4,6-三氯-1,3,5-三嗪与4,4’-二氨基二苯甲烷的聚合物作为前驱体,在模板剂SBA-15的存在下,通过700 oC的热处理碳化,制得有序的氮掺杂介孔碳材料OMCN,并以此为载体,通过液相负载法制备了负载铜纳米颗粒的有序氮掺杂介孔碳材料Cu NPs-OMCN。其次,对所制备的碳材料进行了BET,EA,HRTEM,XRD和XPS等表征,结果表明所制备的前驱体与模板SBA-15之间有较好的融合性,所制备的碳氮材料为有序介孔结构,孔径为4.3 nm,比表面为741 m2/g,氮含量为9.28%。氮原子主要以C-N和N=C的形态存在。电化学性能测试结果表明,本文制备的有序氮掺杂介孔碳材料具有一定的电化学氧还原活性,且负载铜纳米颗粒的有序氮掺杂介孔碳材料Cu NPs-OMCN对氧还原反应的催化性能优于单纯氮掺杂的OMCN材料。最后,本文研究了以负载铜纳米颗粒的氮掺杂介孔碳材料作为催化剂的有机合成反应。在端炔的偶联反应中,以负载铜纳米颗粒的氮掺杂介孔碳材料作为催化剂,碳酸铯为碱,二甲亚砜为溶剂,高效的实现了端炔的自身及交叉偶联反应。在反应中观察到,有序氮掺杂介孔碳材料类似起到了氮配体的效果,是催化剂不可或缺的组成部分,且该催化剂能够实现有效循环,初步实现了固定化配体/功能化载体的设想。基于上述端炔的偶联反应,发展了噻吩、呋喃的一锅法合成反应。以Na2S·9H2O和H2O分别为硫源、氧源,以Cu NPs-OMCN作为催化剂,碳酸铯为碱,二甲亚砜为溶剂,发展了高效、绿色的一锅法噻吩、呋喃及其衍生物的合成反应。综上所述,本文通过简单、廉价的方法制得有序的氮掺杂介孔碳材料,并以此为载体负载铜纳米颗粒作为催化有机合成反应的催化剂;二者均具有电化学氧还原活性。以负载铜纳米颗粒的氮掺杂介孔碳材料作为催化剂,实现了端炔的高效自身及交叉偶联反应,并以此为基础,进一步发展了噻吩、呋喃及其衍生物的一锅法合成反应,且具有良好的官能团容忍性和底物适应性。
[Abstract]:Ordered nitrogen doped mesoporous carbon materials refer to a class of new mesoporous carbon materials containing nitrogen atoms, which are widely used in hydrogen storage materials. Electrode materials and multiphase hydrogenation catalyst carriers, etc., but there are few reports on their application in organic synthesis. In this paper, a novel method for the preparation of ordered nitrogen doped mesoporous carbon materials has been developed and a considerable amount of nitrogen has been prepared. Ordered nitrogen-doped mesoporous carbon materials with good specific surface properties and regular pore size distribution. The supported copper nanoparticles were used as catalysts to realize the self-and cross-coupling reaction of acetylene and the resulting one-pot synthesis of thiophene and furan under mild conditions. Firstly, in the process of preparation of carbon materials, In this paper, an ordered N-doped mesoporous carbon material, OMCNs, was prepared by carbonization of 2C4H4C6-trichloro-3-trichloro-3-triazine and 4C4C- diaminodiphenylmethane by heat treatment at 700oC in the presence of a template agent SBA-15, and was used as the carrier for the synthesis of an ordered N-doped mesoporous carbon material. The ordered nitrogen-doped mesoporous carbon materials Cu NPs-OMCNs were prepared by liquid phase loading method. Secondly, the prepared carbon materials were characterized by BETEAEAA HRTEMU XRD and XPS. The results show that the prepared precursor and template SBA-15 have a good compatibility. The prepared carbon and nitrogen materials have ordered mesoporous structure with a pore size of 4.3 nm, a specific surface area of 741 m2 / g and a nitrogen content of 9.28. The nitrogen atoms mainly exist in the form of C-N and Na-C. The ordered nitrogen-doped mesoporous carbon material prepared in this paper has a certain electrochemical oxygen reduction activity, and the catalytic performance of ordered nitrogen-doped mesoporous carbon material Cu NPs-OMCN for oxygen reduction is superior to that of pure nitrogen-doped mesoporous carbon material. The organic synthesis of nitrogen-doped mesoporous carbon supported on copper nanoparticles was studied in this paper. In the coupling reaction of acetylene, the nitrogen-doped mesoporous carbon supported on copper nanoparticles was used as catalyst and cesium carbonate as base. Dimethyl sulfoxide (DMSO) was used as solvent to efficiently realize the self-and cross-coupling reaction of acetylene. It was observed that the ordered nitrogen-doped mesoporous carbon material played a similar role as a nitrogen ligand and was an indispensable part of the catalyst. Based on the coupling reaction of acetylene terminal, the one-pot synthesis of thiophene and furan was developed. Na2S 9H2O and H _ 2O were used as sulfur source and oxygen source, respectively. Using Cu NPs-OMCN as catalyst, cesium carbonate as base and dimethyl sulfoxide as solvent, the synthesis of thiophene, furan and its derivatives was developed. The ordered nitrogen-doped mesoporous carbon materials were prepared by cheap method and supported on copper nanoparticles as catalysts for organic synthesis. Using nitrogen-doped mesoporous carbon loaded with copper nanoparticles as catalyst, the highly efficient self-coupling and cross-coupling reaction of acetylene was realized, and thiophene was further developed on the basis of the electrochemical oxygen reduction activity. The one-pot synthesis of furan and its derivatives has good functional tolerance and substrate adaptability.
【学位授予单位】：南京航空航天大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ127.11;O621.251

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