基于PDMAEMA复合材料的电化学性能研究

发布时间：2018-01-28 04:58

本文关键词： 聚甲基丙烯酸二甲氨基乙酯多壁碳纳米管多孔碳材料四氧化三铁电化学传感器　出处：《湘潭大学》2015年硕士论文　论文类型：学位论文

【摘要】：环境响应型聚合物聚甲基丙烯酸二甲氨基乙酯(PDMAEMA),其结构中既含有亲水性的叔胺基和羰基,又含有疏水性的烷基基团,在酸性介质中可以被质子化,因而它具有一定的pH值敏感性和温敏性等环境剌激响应的特性。有关PDMAEMA及其嵌段共聚物的合成已经研究得比较多,但是基于PDMAEMA与无机功能材料结合起来的复合材料研究的不多,尤其是基于PDMAEMA的复合材料的电化学研究。因此本论文提出基于PDMAEMA复合材料的制备并研究其相关电化学性能的构思,主要研究内容如下:(1)含PDMAEMA的二嵌段共聚物聚环氧乙烷-b-聚甲基丙烯酸二甲氨基乙酯(PEO-b-PDMAEMA)结合多壁碳纳米管(MWCNTs)的复合材料对亚硝酸钠(NaNO2)电催化研究:将二嵌段共聚物PEO-b-PDMAEMA与MWCNTs结合组成复合材料修饰于玻碳电极上(记为PEO-b-PDMAEMA/MWCNTs/GCE),构建了一种用于测定亚硝酸盐的无酶电化学传感器。实验研究了PEO-b-PDMAEMA温敏性对该传感器性能的影响。随着溶液温度的上升,PEO-b-PDMAEMA/MWCNTs/GCE对亚硝酸盐氧化的电催化作用增强。该传感器显示出对亚硝酸盐浓度较宽的线性检测范围(1.0×10-6至1.0×10-4 M),低的检测限(1.0×10-6 M)和高的灵敏度(562.16μA/mM·cm2)以及良好的稳定性和重复性。(2)基于聚合物PDMAEMA的多孔碳材料(NC)的制备及其对氧气的电催化:因为PDMAEMA中含有C和N元素,以PDMAEMA为碳源和氮源,以KOH为活化物质,采用高温煅烧法将聚合物PDMAEMA热解成为含氮的多孔碳材料(NC)。研究了有无KOH和不同煅烧温度对于材料制备的影响。采用扫描电镜(SEM)、X射线衍射仪(XRD)和比表面积分析仪对所制备的多孔碳材料进行了表征。结果显示,NC具有蜂巢状的多孔结构、高达954 m2/g的比表面积和12.7wt.%的含氮量。实验发现NC修饰的电极对阴极氧还原反应(Oxygen Reduction Reaction,ORR)有较高的电催化活性、优异的循环稳定性和良好的抗甲醇性能。(3)基于聚合物PDMAEMA制备碳包覆磁性纳米四氧化三铁(C/Fe3O4)复合材料及其对双氧水(H2O2)的电催化:采用SEM、EDS、XRD等方法对该复合物的形貌进行了表征。实验表征发现C/Fe3O4为粒径在340 nm左右的球形纳米颗粒,具有良好的导电性能。C/Fe3O4修饰的玻碳电极对H2O2具有良好的电催化活性和低的检测限(3.8×10-7M),以及优异的抗干扰性、稳定性和重现性。
[Abstract]:The environmental responsive polymer PDMAEMAA contains hydrophilic tertiary amine and carbonyl groups as well as hydrophobic alkyl groups. Because it can be protonated in acid medium, it has some characteristics of pH sensitivity and temperature sensitivity. The synthesis of PDMAEMA and its block copolymers has been studied. However, the research of composite materials based on PDMAEMA and inorganic functional materials is not much. Especially the electrochemical study of composites based on PDMAEMA. Therefore, this paper proposed the preparation of PDMAEMA composites and the related electrochemical properties. The main contents of this study are as follows: (1) PDMAEMA diblock copolymer poly (ethylene oxide-b-poly (dimethylamino ethyl methacrylate)-PEO-b-PDMAEMAE). The effect of multiwalled carbon nanotubes (MWCNTs) on sodium nitrite (NaNO2). Electrocatalytic study: the composite material composed of diblock copolymer PEO-b-PDMAEMA and MWCNTs was modified on glassy carbon electrode (. Recorded as PEO-b-PDMAEMA / MWCNTs / GCE. An enzymatic electrochemical sensor for the determination of nitrite was constructed. The effect of PEO-b-PDMAEMA temperature sensitivity on the performance of the sensor was studied. The electrocatalytic effect of PEO-b-PDMAEMA/MWCNTs/GCE on nitrite oxidation was enhanced. The sensor showed a wide linear detection range for nitrite concentration (. From 1.0 脳 10 ~ (-6) to 1.0 脳 10 ~ (-4) M). Low detection limit of 1.0 脳 10 ~ (-6) M) and high sensitivity of 562.16 渭 A / mm 路cm ~ (2) and good stability and repeatability. Preparation of porous carbon material based on polymer PDMAEMA and its electrocatalysis for oxygen: because PDMAEMA contains C and N elements. PDMAEMA was used as carbon and nitrogen source and KOH as activator. The polymer PDMAEMA was pyrolyzed into a porous carbon material containing nitrogen by high temperature calcination. The effects of KOH and different calcination temperature on the preparation of the material were studied by scanning electron microscope (SEM). SEM). The porous carbon materials were characterized by X-ray diffractometer (XRD) and specific surface area analyzer. The specific surface area of 954 m2 / g and the nitrogen content of 12.7 wt.% were obtained. Oxygen Reduction Reaction. ORR) has high electrocatalytic activity. C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 / C / Fe _ 3O _ 4 composites. The electrocatalysis of H _ 2O _ 2 was carried out by SEM. The morphology of the composite was characterized by EDS- XRD. It was found that C / Fe _ 3O _ 4 was spherical nanoparticles with a diameter of about 340 nm. The glassy carbon electrode modified with C / Fe _ 3O _ 4 has good electrocatalytic activity for H2O2, low detection limit of 3.8 脳 10 ~ (-7) MN, and excellent anti-interference. Stability and reproducibility.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB332

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