發(fā)布時(shí)間：2018-08-23 13:08

【摘要】：鄰苯二胺作為一種典型的苯胺衍生物,苯環(huán)鄰位有兩個(gè)相鄰的-NH2,與苯胺相比,鄰苯二胺具有更多的活性位點(diǎn),在后期的加工和修飾方面具有巨大的優(yōu)勢(shì)。由于聚鄰苯二胺獨(dú)特的導(dǎo)電機(jī)制使其在催化、傳感器、電顯色、儲(chǔ)能等方面具有重要的應(yīng)用價(jià)值。目前關(guān)于聚鄰苯二胺材料的研究主要集中在聚合機(jī)理、氧化還原過(guò)程、組裝機(jī)理、光電性質(zhì)和應(yīng)用范圍拓展等方面。聚鄰苯二胺微納米結(jié)構(gòu)的合成方法包括化學(xué)氧化法、共沉淀法、微流控法、水熱法等。特殊形貌聚鄰苯二胺微納米結(jié)構(gòu)的合成及其應(yīng)用研究是聚鄰苯二胺研究中的熱點(diǎn)問(wèn)題。本文以鄰苯二胺為主要研究對(duì)象,利用化學(xué)氧化法和電形成的方法成功制備出了不同形貌的聚鄰苯二胺微納米結(jié)構(gòu),并對(duì)其形貌進(jìn)行調(diào)控。利用所制備的聚鄰苯二胺,研究其經(jīng)過(guò)不同的后處理過(guò)程后的去組裝和熒光現(xiàn)象,也研究了其在pH熒光探針、電催化和超級(jí)電容器等方面的應(yīng)用。以CuCl_2為氧化劑,利用化學(xué)氧化法成功制備了聚鄰苯二胺微納米結(jié)構(gòu)。在聚合的過(guò)程中,由于聚鄰苯二胺低聚體之間的靜電排斥作用聚鄰苯二胺低聚體并未發(fā)生自組裝過(guò)程。在反應(yīng)體系中引入高鹽溶液,提高溶液中的離子強(qiáng)度,促進(jìn)了聚鄰苯二胺低聚體的自組裝過(guò)程。通過(guò)對(duì)反應(yīng)中物料摩爾比的控制,分別得到了聚鄰苯二胺帶狀、纖維狀、納米束、團(tuán)簇狀、超長(zhǎng)纖維等一系列結(jié)構(gòu)。通過(guò)對(duì)實(shí)驗(yàn)結(jié)果進(jìn)行分析,提出了聚鄰苯二胺的生成機(jī)理。研究了質(zhì)子化和去質(zhì)子化過(guò)程對(duì)聚鄰苯二胺形貌的影響。聚鄰苯二胺超長(zhǎng)纖維經(jīng)過(guò)去質(zhì)子化過(guò)程,在紫外光(λ_(ex)=418nm)激發(fā)下能發(fā)出綠色的熒光,熒光效率高達(dá)56.2%。利用聚鄰苯二胺超長(zhǎng)纖維對(duì)去質(zhì)子化過(guò)程的敏感性,研究了其作為pH熒光探針的性能。p H熒光探針對(duì)紫外光的抗漂白性良好。聚鄰苯二胺pH熒光探針具有良好的穩(wěn)定性。為了排除重金屬離子對(duì)聚鄰苯二胺自組裝過(guò)程的影響,以綠色氧化劑H_2O_2為氧化劑,利用化學(xué)氧化法成功制備了聚鄰苯二胺微納米結(jié)構(gòu)。聚合過(guò)程中利用NaCl提高溶液的離子強(qiáng)度,促進(jìn)聚鄰苯二胺低聚體的聚合。合成的結(jié)構(gòu)包括矩形內(nèi)方纖維、球狀、球狀團(tuán)簇、海膽狀等一系列聚鄰苯二胺微納米結(jié)構(gòu)。通過(guò)對(duì)反應(yīng)條件的控制,實(shí)現(xiàn)了對(duì)聚鄰苯二胺纖維長(zhǎng)度、寬度、彎曲和分叉等精細(xì)結(jié)構(gòu)的控制。H_2O_2為氧化劑通過(guò)化學(xué)氧化法可制備聚對(duì)苯二胺,證明該合成方法能夠?qū)崿F(xiàn)聚對(duì)苯二胺形貌的調(diào)控。通過(guò)各種后處理的方法對(duì)聚鄰苯二胺進(jìn)行去組裝,對(duì)其去組裝過(guò)程進(jìn)行了建模。研究了去質(zhì)子化過(guò)程后聚鄰苯二胺熒光纖維的熒光性能。利用高溫煅燒的方法調(diào)節(jié)聚鄰苯二胺材料中的C/N比,從而制備了聚鄰苯二胺電極材料,并研究了其在超級(jí)電容器方面的性能。S-400、S-500、S-600電極的循環(huán)穩(wěn)定性隨著循環(huán)次數(shù)的增加損失明顯。S-700和S-800電極經(jīng)過(guò)1000次循環(huán)之后,電容約為初始電容的95%,穩(wěn)定性良好。在聚鄰苯二胺微納米結(jié)構(gòu)的制備過(guò)程中引入貴金屬氧化劑H_2PdCl_4,并成功制備了Pd摻雜聚鄰苯二胺微納米結(jié)構(gòu)。合成的結(jié)構(gòu)包括矩形內(nèi)方管狀、六方管狀、帶狀和球狀等一系列Pd摻雜聚鄰苯二胺微納米結(jié)構(gòu)。通過(guò)對(duì)反應(yīng)條件的控制實(shí)現(xiàn)了Pd摻雜聚鄰苯二胺微納米結(jié)構(gòu)的控制,并研究了聚鄰苯二胺矩形內(nèi)方管的生成過(guò)程。Pd摻雜的聚鄰苯二胺矩形內(nèi)方管經(jīng)過(guò)高溫煅燒后,生成由大量Pd顆粒組成的矩形內(nèi)方Pd管,并研究了矩形內(nèi)方Pd管對(duì)乙醇的電催化性能。商業(yè)Pt/C催化劑的EASA值為26.7m2/g,SP-Pd-MTs的EASA值為48.2m2/g。SP-Pd-MTs的EASA值較大,可能是因?yàn)镾P-Pd-MTs管壁中存在大量的孔洞結(jié)構(gòu)。SP-Pd-MTs催化劑的正向掃描的氧化還原電流密度為146mA/cm2,而商業(yè)Pt/C催化劑的電流密度僅為48.5mA/cm2。SP-Pd-MTs催化劑的電流密度和EASA值都比商業(yè)Pt/C催化劑大,說(shuō)明SP-Pd-MTs催化劑對(duì)乙醇具有良好的電催化性。在聚鄰苯二胺的自組裝過(guò)程中引入電場(chǎng)來(lái)控制聚鄰苯二胺低聚體的自組裝過(guò)程,并成功得到了聚鄰苯二胺半閉合管狀結(jié)構(gòu)。通過(guò)改變電極距離和電場(chǎng)形狀實(shí)現(xiàn)了聚鄰苯二胺結(jié)構(gòu)的控制。隨著兩電極距離的增大,聚鄰苯二胺的管狀結(jié)構(gòu)逐漸消失。在勻強(qiáng)電場(chǎng)下,聚鄰苯二胺低聚體組裝成為聚鄰苯二胺纖維。利用COMSOL Multiphysics軟件對(duì)電場(chǎng)進(jìn)行了模擬,并提出了聚鄰苯二胺半閉合管的形成機(jī)理。聚鄰苯二胺半管經(jīng)過(guò)去質(zhì)子化處理后,聚鄰苯二胺半管發(fā)出綠色熒光。經(jīng)過(guò)乙醇處理后,發(fā)出強(qiáng)紅色熒光。綠色熒光和紅色熒光效率分別為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.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.1;O633.21

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