聚邻苯二胺微纳米结构制备及其应用研究

发布时间：2018-08-23 13:08

【摘要】：邻苯二胺作为一种典型的苯胺衍生物,苯环邻位有两个相邻的-NH2,与苯胺相比,邻苯二胺具有更多的活性位点,在后期的加工和修饰方面具有巨大的优势。由于聚邻苯二胺独特的导电机制使其在催化、传感器、电显色、储能等方面具有重要的应用价值。目前关于聚邻苯二胺材料的研究主要集中在聚合机理、氧化还原过程、组装机理、光电性质和应用范围拓展等方面。聚邻苯二胺微纳米结构的合成方法包括化学氧化法、共沉淀法、微流控法、水热法等。特殊形貌聚邻苯二胺微纳米结构的合成及其应用研究是聚邻苯二胺研究中的热点问题。本文以邻苯二胺为主要研究对象,利用化学氧化法和电形成的方法成功制备出了不同形貌的聚邻苯二胺微纳米结构,并对其形貌进行调控。利用所制备的聚邻苯二胺,研究其经过不同的后处理过程后的去组装和荧光现象,也研究了其在pH荧光探针、电催化和超级电容器等方面的应用。以CuCl_2为氧化剂,利用化学氧化法成功制备了聚邻苯二胺微纳米结构。在聚合的过程中,由于聚邻苯二胺低聚体之间的静电排斥作用聚邻苯二胺低聚体并未发生自组装过程。在反应体系中引入高盐溶液,提高溶液中的离子强度,促进了聚邻苯二胺低聚体的自组装过程。通过对反应中物料摩尔比的控制,分别得到了聚邻苯二胺带状、纤维状、纳米束、团簇状、超长纤维等一系列结构。通过对实验结果进行分析,提出了聚邻苯二胺的生成机理。研究了质子化和去质子化过程对聚邻苯二胺形貌的影响。聚邻苯二胺超长纤维经过去质子化过程,在紫外光(λ_(ex)=418nm)激发下能发出绿色的荧光,荧光效率高达56.2%。利用聚邻苯二胺超长纤维对去质子化过程的敏感性,研究了其作为pH荧光探针的性能。p H荧光探针对紫外光的抗漂白性良好。聚邻苯二胺pH荧光探针具有良好的稳定性。为了排除重金属离子对聚邻苯二胺自组装过程的影响,以绿色氧化剂H_2O_2为氧化剂,利用化学氧化法成功制备了聚邻苯二胺微纳米结构。聚合过程中利用NaCl提高溶液的离子强度,促进聚邻苯二胺低聚体的聚合。合成的结构包括矩形内方纤维、球状、球状团簇、海胆状等一系列聚邻苯二胺微纳米结构。通过对反应条件的控制,实现了对聚邻苯二胺纤维长度、宽度、弯曲和分叉等精细结构的控制。H_2O_2为氧化剂通过化学氧化法可制备聚对苯二胺,证明该合成方法能够实现聚对苯二胺形貌的调控。通过各种后处理的方法对聚邻苯二胺进行去组装,对其去组装过程进行了建模。研究了去质子化过程后聚邻苯二胺荧光纤维的荧光性能。利用高温煅烧的方法调节聚邻苯二胺材料中的C/N比,从而制备了聚邻苯二胺电极材料,并研究了其在超级电容器方面的性能。S-400、S-500、S-600电极的循环稳定性随着循环次数的增加损失明显。S-700和S-800电极经过1000次循环之后,电容约为初始电容的95%,稳定性良好。在聚邻苯二胺微纳米结构的制备过程中引入贵金属氧化剂H_2PdCl_4,并成功制备了Pd掺杂聚邻苯二胺微纳米结构。合成的结构包括矩形内方管状、六方管状、带状和球状等一系列Pd掺杂聚邻苯二胺微纳米结构。通过对反应条件的控制实现了Pd掺杂聚邻苯二胺微纳米结构的控制,并研究了聚邻苯二胺矩形内方管的生成过程。Pd掺杂的聚邻苯二胺矩形内方管经过高温煅烧后,生成由大量Pd颗粒组成的矩形内方Pd管,并研究了矩形内方Pd管对乙醇的电催化性能。商业Pt/C催化剂的EASA值为26.7m2/g,SP-Pd-MTs的EASA值为48.2m2/g。SP-Pd-MTs的EASA值较大,可能是因为SP-Pd-MTs管壁中存在大量的孔洞结构。SP-Pd-MTs催化剂的正向扫描的氧化还原电流密度为146mA/cm2,而商业Pt/C催化剂的电流密度仅为48.5mA/cm2。SP-Pd-MTs催化剂的电流密度和EASA值都比商业Pt/C催化剂大,说明SP-Pd-MTs催化剂对乙醇具有良好的电催化性。在聚邻苯二胺的自组装过程中引入电场来控制聚邻苯二胺低聚体的自组装过程,并成功得到了聚邻苯二胺半闭合管状结构。通过改变电极距离和电场形状实现了聚邻苯二胺结构的控制。随着两电极距离的增大,聚邻苯二胺的管状结构逐渐消失。在匀强电场下,聚邻苯二胺低聚体组装成为聚邻苯二胺纤维。利用COMSOL Multiphysics软件对电场进行了模拟,并提出了聚邻苯二胺半闭合管的形成机理。聚邻苯二胺半管经过去质子化处理后,聚邻苯二胺半管发出绿色荧光。经过乙醇处理后,发出强红色荧光。绿色荧光和红色荧光效率分别为40.5%和52.4%,且具有良好的抗漂白性。
[Abstract]:As a typical aniline derivative, o-phenylenediamine has two adjacent sites - NH2. Compared with aniline, o-phenylenediamine has more active sites and has great advantages in later processing and modification. At present, the research on poly (o-phenylenediamine) mainly focuses on the polymerization mechanism, oxidation-reduction process, assembly mechanism, photoelectric properties and application scope. The synthesis methods of poly (o-phenylenediamine) Micro-Nanostructures include chemical oxidation method, coprecipitation method, microfluidic method, hydrothermal method and so on. The synthesis and application of micro-and nano-structures is a hot topic in the study of poly (o-phenylenediamine). In this paper, o-phenylenediamine was used as the main object of study. Different morphologies of micro-and nano-structures of poly (o-phenylenediamine) were successfully prepared by chemical oxidation and electroforming methods, and their morphologies were controlled. The disassembly and fluorescence phenomena of poly(o-phenylenediamine) after different post-treatment processes were investigated, and their applications in pH fluorescence probes, electrocatalysis and supercapacitors were also investigated. CuCl_2 was used as oxidant to prepare poly(o-phenylenediamine) Micro-Nanostructures by chemical oxidation method. Poly (o-phenylenediamine) oligomers do not undergo self-assembly due to electro-repulsion. Introducing high salt solution into the reaction system improves the ionic strength of the solution and promotes the self-assembly of poly (o-phenylenediamine) oligomers. The formation mechanism of poly (o-phenylenediamine) was proposed based on the analysis of the experimental results. The effects of protonation and depolymerization on the morphology of poly (o-phenylenediamine) were studied. The green fluorescence and fluorescence of the ultra-long poly (o-phenylenediamine) fiber excited by ultraviolet light (lambda (ex) = 418 nm) were observed after depolymerization. The efficiency is up to 56.2%. The properties of the poly (o-phenylenediamine) super-long fiber as a pH fluorescent probe have been studied by using its sensitivity to the depolymerization process. The poly (o-phenylenediamine) pH fluorescent probe has good bleaching resistance to ultraviolet light. The poly (o-phenylenediamine) pH fluorescent probe has good stability. Poly (o-phenylenediamine) micro-and nano-structures were successfully prepared by chemical oxidation using green oxidant H_2O_2 as oxidant. NaCl was used to enhance the ionic strength of the solution and promote the polymerization of poly (o-phenylenediamine) oligomers during the polymerization process. Nanostructures. Fine structures such as length, width, bending and bifurcation of poly (o-phenylenediamine) fibers can be controlled by controlling reaction conditions. Poly (o-phenylenediamine) can be prepared by chemical oxidation with H_2O_2 as oxidant, which proves that the synthesis method can realize the morphology control of poly (o-phenylenediamine). The morphology of poly (o-phenylenediamine) can be controlled by various post-treatment methods. The fluorescence properties of poly(o-phenylenediamine) fluorescent fibers after depolymerization were studied. The C/N ratio of poly(o-phenylenediamine) was adjusted by calcination at high temperature. The poly(o-phenylenediamine) electrode material was prepared and its performance in supercapacitor was studied. After 1000 cycles, the capacitance of S-700 and S-800 electrodes was about 95% of the initial capacitance, and the stability was good. The precious metal oxidant H_2PdCl_4 was introduced into the preparation of poly (o-phenylenediamine) Micro-Nanostructures and the Pd-doped poly (o-phenylenediamine) micro-structures were successfully prepared. Nanostructures. A series of Pd-doped poly (o-phenylenediamine) micro-and nanostructures were synthesized, including rectangular, hexagonal, banded and spherical structures. The Pd-doped poly (o-phenylenediamine) micro-and nanostructures were controlled by controlling the reaction conditions. The formation process of poly (o-phenylenediamine) rectangular inner square tubes was studied. A rectangular inner square Pd tube with a large number of Pd particles was formed after calcination of diamine rectangular inner square tube at high temperature. The electrocatalytic performance of rectangular inner square Pd tube for ethanol was studied. The EASA value of commercial Pt/C catalyst was 26.7 m2/g, and that of SP-Pd-MTs was 48.2 m2/g. The current density and EASA value of SP-Pd-MTs catalyst were higher than those of commercial Pt/C catalyst, indicating that SP-Pd-MTs catalyst had good electrocatalytic activity for ethanol. The semi-closed tubular structure of poly (o-phenylenediamine) was successfully obtained by introducing an electric field to control the self-assembly process of poly (o-phenylenediamine) oligomers. The structure of poly (o-phenylenediamine) was controlled by changing the electrode distance and the shape of the electric field. Poly (o-phenylenediamine) oligomers were assembled into poly (o-phenylenediamine) fibers. The electric field was simulated by COMSOL Multiphysics software and the formation mechanism of poly (o-phenylenediamine) semi-closed tubes was proposed. The poly (o-phenylenediamine) semi-tubes emitted green fluorescence after protonation treatment. The poly (o-phenylenediamine) semi-tubes emitted strong red after ethanol treatment. Fluorescence, green fluorescence and red fluorescence efficiency were 40.5% and 52.4% respectively, and had good bleaching resistance.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB383.1;O633.21

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