功能化多孔碳材料的制备及其应用研究

发布时间：2018-07-18 16:12

【摘要】：多孔碳材料由于其独特的结构和性质引起了人们的广泛关注并在吸附、分离、催化及电化学等方面展现了优异的应用性能。通过选择合适的合成条件与方法,可对其进行形貌及结构的可控制备。但纯的多孔碳材料表面存在一定惰性,反应活性低,为提高化学活性位,可通过引入杂原子对其进行功能化修饰,从而进一步提高碳材料的物理和化学性能,使其具有更加广阔的应用发展前景。论文的主要研究内容如下:1)提出一种简单而独特的制备具有二维六方有序结构的介孔碳的方法,即“热解-沉积”法。该方法以树脂聚合物在高温碳化中释放的尾气为碳源,铁修饰的SBA-15为模板剂,将树脂聚合物和SBA-15模板放在同一个通氮气的碳化炉中碳化。在碳化过程中,树脂聚合物热解释放出的尾气随着氮气可同时被沉积并捕获到SBA-15模板的孔道结构中,在铁的催化下合成MCs。并对该介孔碳材料在6 mol L-1 KOH溶液中进行了其电化学性质的研究,探讨其做为电极材料的超级电容器的性能。2)以间氨基苯酚为碳、氮源,正硅酸乙酯为结构辅助剂,十六烷基三甲基溴化铵做为表面活性剂,在氨水的催化下,通过“硅助剂”的方法一步制备高度分散且粒径均匀可调的氮掺杂中空介孔碳球。该方法以间氨基苯酚同时做为碳源和氮源原位地对中空碳球进行氮掺杂实现功能化修饰,并研究溶液中乙醇、水的体积比,对所制备的N-HMCSs的直径、空腔直径、壁厚的影响。而且考察氮掺杂中空介孔碳球做为电极材料的超级电容器性能,探讨对材料进行氮掺杂后对其电容性能的影响。3)提出了一种简单、可行的一步溶胶-凝胶法制备了粒径和形貌可调的氮掺杂的中空介孔碳球。在这个合成过程中,树脂做为碳源,正硅酸乙酯做为结构助剂,咪唑类离子液体(1-alkyl-3-methylimidazolium bromide,[CnMim]Br,n=4,8,12,16)具有“三合一”的作用,即不仅做为软模板又做为氮源和部分碳源。该方法根据离子液体掺氮的性质及离子液体在碱性溶液中与带负电荷的二氧化硅低聚物、树脂集聚体之间较强的静电相互作用,一步原位的合成了氮掺杂的中空介孔碳球。通过改变离子液体的量研究其对所制备的N-HMCSs粒径、形貌、结构、均匀性的影响。同时通过改变离子液体烷基链的长度,探究烷基链的长度对N-HMCSs形貌形成的作用,并考察氮掺杂的中空介孔碳球用作超级电容器电极材料的电化学性能。
[Abstract]:Porous carbon materials have attracted wide attention due to their unique structure and properties, and have shown excellent applications in adsorption, separation, catalysis and electrochemistry. The morphology and structure can be controlled by selecting suitable synthesis conditions and methods. However, the surface of pure porous carbon materials is inert and the reaction activity is low. In order to improve the chemical active sites, the physical and chemical properties of carbon materials can be further improved by introducing hetero-atoms to functionalize them. So that it has a broader application and development prospects. The main contents of this paper are as follows: (1) A simple and unique method for preparing mesoporous carbon with two-dimensional hexagonal ordered structure is proposed, which is called "pyrolysis-deposition" method. In this method, the tail gas released by resin polymer in high temperature carbonation was used as carbon source, and the ferric modified SBA-15 was used as template. The resin polymer and SBA-15 template were carbonated in the same nitrogen carbonization furnace. During carbonation, the tail gas released from the pyrolysis of the resin polymer can be deposited simultaneously with nitrogen and trapped in the pore structure of SBA-15 template, and then synthesized by the catalysis of iron. The electrochemical properties of the mesoporous carbon material in 6 mol L-1 Koh solution were studied. The performance of the supercapacitor as electrode material was discussed. The mesoporous carbon was composed of m-aminophenol as carbon, nitrogen source and ethyl orthosilicate as structural auxiliary agent. Using cetyltrimethylammonium bromide as a surfactant and catalyzed by ammonia, N-doped hollow mesoporous carbon spheres with highly dispersed and uniform particle size were prepared by the method of "silicon promoter". In this method, m-aminophenol was used as carbon source and nitrogen source to functionalize the hollow carbon spheres in situ, and the effects of the volume ratio of ethanol and water in solution on the diameter, cavity diameter and wall thickness of N-HMCSs were studied. Furthermore, a simple method was proposed to investigate the performance of nitrogen doped hollow mesoporous carbon ball as electrode material and to investigate the effect of nitrogen doping on the capacitance performance of the supercapacitor. Nitrogen doped hollow mesoporous carbon spheres with adjustable particle size and morphology were prepared by one step sol-gel method. In this process, resin is used as carbon source, tetraethyl orthosilicate as structural assistant, and imidazole ionic liquid ([CnMim] Brnbumin 4CnMim) has the function of "three-in-one", which is not only used as a soft template, but also as a nitrogen source and a part of carbon source. According to the properties of nitrogen-doped ionic liquids and the strong electrostatic interaction between ionic liquids and negatively charged silica oligomers and resin aggregates, nitrogen-doped hollow mesoporous carbon spheres were synthesized in one step in situ. The effects of ionic liquids on the particle size, morphology, structure and homogeneity of N-HMCSs were studied by changing the amount of ionic liquids. The effects of alkyl chain length on the morphology of N-HMCSs were investigated by changing the length of ionic liquid alkyl chain. The electrochemical properties of N-doped hollow mesoporous carbon spheres as electrode materials for supercapacitor were investigated.
【学位授予单位】：河北科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ127.11;TB383.4

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