本文關(guān)鍵詞： 單壁碳納米管 共軛聚合物 雙水相 分離 半導(dǎo)體/金屬 窄手性　出處：《合肥工業(yè)大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：單壁碳納米管(Single-Walled Carbon Nanotubes, SWCNTs)具有優(yōu)異的電學(xué)、力學(xué)、光學(xué)性能,因此具有非常大的潛力應(yīng)用于納米器件、傳感器、透明導(dǎo)電薄膜和復(fù)合材料等領(lǐng)域。但目前通過正常的制備方法還無(wú)法得到單一導(dǎo)電屬性和電子結(jié)構(gòu)的SWCNTs.因此,如何快速有效地分離金屬性(m)-SWCNTs和半導(dǎo)體性(s)-SWCNTs,并且得到高純度的s-SWCNTs和各種手性的SWCNTs,成為當(dāng)前碳納米管研究工作所面臨的巨大挑戰(zhàn)。共軛聚合物的選擇性分離是一種重要的分離手段,主要是通過SWCNTs與聚合物之間的π-π相互作用進(jìn)行分離,用于分離SWCNTs的聚合物可以分為三類：芴基聚合物、噻吩基聚合物和咔唑基聚合物,此方法可以得到高純度的s-SWCNTs,這對(duì)諸多高端科技領(lǐng)域的傳感器、電子器件、場(chǎng)效應(yīng)晶體管(FETs)是極其重要的。另外,利用雙水相法分離SWCNTs,分離過程中不會(huì)破壞SWCNTs的本征結(jié)構(gòu),并且設(shè)備簡(jiǎn)易、流程簡(jiǎn)單、方便、時(shí)間短,有望實(shí)現(xiàn)SWCNTs的宏量分離,具有很好的發(fā)展前景。本文研究的主要內(nèi)容如下：(1)首先選取四種不同種類的原始SWCNTs,利用熱重分析(TG)、場(chǎng)發(fā)射電子顯微鏡(SEM)、紫外-可見光-紅外(UV-vis-IR)吸收光譜、Raman光譜和原子力顯微鏡(AFM)表征方法對(duì)碳管原料進(jìn)行定性的表征,了解每種SWCNTs的基本特征,選擇HiPCO和arc-SWCNTs作為接下來(lái)分離的原料碳管。(2)基于共軛聚合物的非共價(jià)鍵選擇性分離,設(shè)計(jì)合成了三種基于咔唑的共軛聚合物。首先探究了不同溶劑對(duì)聚合物分散arc-SWCNTs的影響,我們發(fā)現(xiàn)在極性最大的四氫呋喃中分散的SWCNTs濃度最高但沒有選擇性；在極性適中的鄰二甲苯中,可以分離出高純度的s-SWCNTs;在極性比較小的甲苯中,分散劑對(duì)SWCNTs溶解度最小,但對(duì)s-SWCNTs有一定的選擇性。原因主要是不同極性的溶劑,導(dǎo)致高分子量的聚合物在溶液中改變自身構(gòu)型。然后探究了不同結(jié)構(gòu)的共軛聚合物對(duì)分散arc-SWCNTs的影響,發(fā)現(xiàn)PCO對(duì)半導(dǎo)體碳管的選擇性最好,PCP對(duì)半導(dǎo)體碳管的選擇性也非常好,并且它更傾向于選擇直徑較小的s-SWCNTs,而PCBP對(duì)s-SWCNTs的選擇性最差。原因是吡啶結(jié)構(gòu)的加入影響聚合物的幾何構(gòu)型和聚合物與SWCNTs之間的能量匹配。(3)采取雙水相分離法,利用幾種不同的表面活性劑,成功分離了不同導(dǎo)電屬性的arc-SWCNTs和不同導(dǎo)電屬性、直徑、窄手性的HiPCO-SWCNTs.首先利用膽酸鈉(SC)、十二烷基硫酸鈉(SDS)和硫氰化鈉(NaSCN)鹽在20℃下分離s/m-SWCNTs,闡述了二次分離的方法提純SWCNTs和兩種富集碳管的方法,以及擴(kuò)大濃度、體積的可實(shí)施性�；赟C和脫氧膽酸鈉(DOC)的ATP體系對(duì)HiPCO-SWCNTs的選擇性不同,進(jìn)行SC、SDS以及NaSCN對(duì)s/m-SWCNTs表面親疏水性調(diào)制,實(shí)現(xiàn)了HiPCO-SWCNTs的m/s分離。隨后進(jìn)一步通過精確控制DOC和SDS表面活性劑濃度,聯(lián)合連續(xù)多步分離策略,實(shí)現(xiàn)了高純度的不同直徑和窄手性的s-SWCNTs分離。
[Abstract]:Single-Walled Carbon Nanotubeses (SWCNTs) have excellent electrical, mechanical and optical properties. Therefore, there is a great potential to be used in nanodevices, sensors. Transparent conductive thin films and composite materials. But through the normal preparation method can not get a single conductive properties and electronic structure of SWCNTs. therefore. The high purity s-SWCNTs and various chiral SWCNTs can be obtained by separating the gold attributes (MS-SWCNTs) and semiconductive sapphire SWCNTs quickly and effectively. The selective separation of conjugated polymers is an important means of separation. It is mainly separated by 蟺-蟺 interaction between SWCNTs and polymer. The polymers used to separate SWCNTs can be divided into three types: fluorene polymer. Thiophene based polymers and carbazolyl polymers can be obtained by this method with high purity s-SWCNTswhich are used for many high-end science and technology fields of sensors and electronic devices. Field effect transistor (FET) is very important. In addition, the separation of SWCNTs by two-phase water method will not destroy the intrinsic structure of SWCNTs during the separation process, and the equipment is simple and the flow is simple. Convenient, short time, it is expected to achieve macro separation of SWCNTs, which has a good development prospects. The main contents of this paper are as follows: 1) first of all, four different kinds of original SWCNTs are selected. Thermogravimetric analysis (TGN), field emission electron microscopy (EEM) and UV-vis-IR (UV-vis IR) absorption spectra were used. Raman spectra and atomic force microscopy (AFM) characterization methods were used to characterize carbon tube materials qualitatively and to understand the basic characteristics of each kind of SWCNTs. HiPCO and arc-SWCNTs were selected as the next raw materials for the separation of carbon tubes. 2) Non-covalent bond selective separation based on conjugated polymers. Three kinds of conjugated polymers based on carbazole were designed and synthesized. Firstly, the effects of different solvents on polymer dispersed arc-SWCNTs were investigated. We found that the concentration of dispersed SWCNTs in tetrahydrofuran with the highest polarity was the highest but no selectivity. High purity s-SWCNTscan be separated from o-xylene with moderate polarity. In toluene with low polarity, the solubility of dispersant to SWCNTs is the least, but the selectivity to s-SWCNTs is certain. The main reason is the solvent with different polarity. The effects of conjugated polymers with different structures on the dispersion of arc-SWCNTs were investigated. It is found that the selectivity of PCO to semiconductor carbon tubes is the best and the selectivity of PCO to semiconductor carbon tubes is also very good, and it is more inclined to choose s-SWCNTs with smaller diameters. The selectivity of PCBP to s-SWCNTs was the worst, because the addition of pyridine affected the geometry of polymer and the energy match between polymer and SWCNTs. Two water phase separation method is adopted. Using several kinds of surfactants, the arc-SWCNTs with different conductive properties and different conductive properties, diameters were successfully separated. Narrow chiral HiPCO-SWCNTs. first, sodium cholate was used. S / m -SWCNTs were separated by sodium 12 alkyl sulfate (SDS) and sodium thiocyanate (NaSCN) at 20 鈩，

本文編號(hào)：1475140