本文關(guān)鍵詞：兩親型杯芳烴合成及其對ZnO微納結(jié)構(gòu)調(diào)控研究　出處：《揚州大學》2016年碩士論文　論文類型：學位論文

  更多相關(guān)文章： 杯芳烴 表面活性劑 氧化鋅 微納材料 光催化

【摘要】：杯芳烴作為超分子主體化合物,其獨特的空腔大環(huán)結(jié)構(gòu),為眾多化學研究提供了有利環(huán)境而備受矚目。近年來,間苯二酚杯芳烴因其合成簡單,優(yōu)異的物理和化學性質(zhì),并且通過兩親功能修飾,其在分子識別、熒光探針、藥物包埋、自組裝有序組合體以及納米材料合成方面具有顯著應用。而功能化修飾后的杯芳烴可以作為保護劑和誘導劑調(diào)控不同形貌和尺寸的微納材料的制備,則是一個極為有意義的探索,將為微納材料的調(diào)控提供新思路、新方法,是值得研究的課題。本文從膠體與界面化學的原理出發(fā),合成了一種新穎的兩親型杯芳烴型表面活性劑,對其理化性質(zhì)進行了表征與分析,并成功將其運用于調(diào)控ZnO微納材料的制備中,實現(xiàn)了球狀ZnO和花狀ZnO的合成,并對形成機理、理化性質(zhì)以及光催化應用等方面進行了應用研究。在球狀ZnO微納材料的調(diào)控和性質(zhì)研究實驗中,主要討論了反應條件對形貌的影響,并重點考察了其形成機理,接著對其光催化性能進行分析,提出催化機制；在花狀ZnO的調(diào)控制備中,重點探討了硝酸鋅和表面活性劑的用量對形貌和尺寸的影響,接著對其光催化降解甲基紫溶液進行研究,對其表現(xiàn)出較好催化性進行了重點分析,提出催化機制。實驗中制備的微納材料形貌及結(jié)構(gòu)性質(zhì)分別通過SEM、TEM、XRD、TG、FT-IR等測試手段進行表征和分析。本文的主要研究內(nèi)容如下：1、本文首先以間苯二酚為原料,參照文獻方法合成了間苯二酚杯[4]芳烴,再在杯芳烴C-2位置上引入醛基,接著與丙二酸二甲酯反應,并水解獲得了目標產(chǎn)物間苯二酚杯[4]芳烴羧酸(TTCC),利用核磁共振、紅外等手段對產(chǎn)物進行了表征,同時對其水溶液進行了研究。通過起泡和穩(wěn)泡性能測試結(jié)果,我們發(fā)現(xiàn),TTCC表面活性劑具有很好的起泡和穩(wěn)泡性能,利用吊片法和電導率法對其臨界膠束濃度進行了測定,具有較低的臨界膠束濃度,為0.13 mM,測定結(jié)果與熒光光譜以及紫外可見光譜結(jié)果一致。2、利用兩親型杯芳烴TTCC表面活性劑為保護劑,硝酸鋅為鋅源,氨水為絡(luò)合劑,通過簡單常壓回流的方法制備了形貌和尺寸均一的ZnO微球,其直徑在800-1000 nm范圍內(nèi),是由20-30 nm的納米顆粒在TTCC的誘導下組裝而成。ZnO微球的XRD表征該樣品為六角纖鋅礦結(jié)構(gòu),并考察了不同反應條件對樣品形貌和尺寸的影響。研究發(fā)現(xiàn),煅燒后的白色ZnO具有介孔結(jié)構(gòu),TTCC表面活性劑在樣品的合成過程中不僅起到了調(diào)控納米材料的形貌作用,同時還參與其骨架組成,結(jié)果分別得到了SEM、TEM、TG以及FT-IR等驗證。采用甲基紫水溶液為模型反應,評價了ZnO的光催化活性。結(jié)果表明,800℃煅燒前后的ZnO對甲基紫染料均表現(xiàn)出很好的光催化效果。3、利用兩親型杯芳烴間苯二酚己基杯[4]芳烴(TTO)為誘導劑,硝酸鋅為鋅源,氨水為絡(luò)合劑,同樣利用簡單回流方法制備出了形貌和尺寸均一花狀ZnO微納結(jié)構(gòu),通過SEM、TEM可知花狀ZnO的粒徑約為1μm,花瓣是由長度500 nm,寬為200 nm的納米片組成。XRD結(jié)果顯示合成的樣品具有六角纖鋅礦結(jié)構(gòu),且是沿著(002)晶面生長,其結(jié)果也得到了HR-TEM照片的驗證。TG結(jié)果表明TTO在花狀ZnO的合成過程中不僅起到了很好的誘導作用,同時可能與ZnO形成某種作用力吸附在其表面而呈現(xiàn)粉色,結(jié)果得到了接觸角測定結(jié)果的支撐。接著考察了不同TTO及硝酸鋅用量對花狀ZnO形貌和尺寸的影響。運用FT-IR及UVDRS對花狀ZnO的光學性能進行測試,結(jié)果表明花狀ZnO不僅可以吸收紫外光,同時也可吸收可見光。在對甲基紫染料的光降解實驗中表現(xiàn)出很高的催化活性,紫外光照射18 min,脫色率可達96.6%,可見光照射270 min,脫色率可到67.9%。半導體金屬氧化物光催化降解染料主要與其缺陷有關(guān),接著運用Raman、PL以及XPS對其缺陷進行表征,結(jié)果顯示花狀ZnO確實具有較高濃度的氧空位。
[Abstract]:Calixarene is a supramolecular compound, its unique cavity ring structure, for many chemical research provides a favorable environment has attracted attention. In recent years, resorcarene because of its simple synthesis, excellent physical and chemical properties, and through the two Pro function modification in molecular recognition, fluorescent probe, drug embedding. Self assembly combination and synthesis of nano materials has significant application. The functionalized calixarenes can be used as protective agent and agent induced by manipulating the morphology and size of micro nano material preparation, is a very meaningful exploration, the new method will provide new ideas for micro regulation the material, is a topic worthy of study. From the principle of colloid and Interface Chemistry, a novel two - calixarene surfactant was synthesized, its physicochemical properties were characterized and analyzed, and The power applied to the regulation of ZnO micro nano material preparation, the synthesis of spherical flower like ZnO and ZnO, and the formation mechanism, the application of physical and chemical properties and photocatalytic application. In spherical ZnO micro nano materials control and properties of the experiment, mainly discussed the influence of reaction conditions on the morphology, and investigated its formation mechanism, then analyses its photocatalytic properties, catalytic mechanism is proposed; in the control of flower like ZnO preparation, discussed the influence of zinc nitrate and the amount of surfactant on the morphology and size, then study on the photocatalytic degradation of methyl violet solution. The better catalytic properties were analyzed. The proposed catalytic mechanism. The preparation of micro nano materials morphology and structural properties respectively by SEM, TEM, XRD, TG, FT-IR were characterized and analyzed. The main research of this paper. The contents are as follows: 1. This paper was synthesized from resorcin resorcin [4] arene synthesized according to the literature, and then introduce aldehyde in calixarene C-2 position, and then two methyl malonic acid hydrolysis reaction, and obtain the target product of resorcin [4] arene carboxylic acid (TTCC), nuclear magnetic resonance, the product the characterization of IR, and the aqueous solution was studied. The foaming and foam stabilization performance test results, we found that the TTCC surfactant has good foaming performance and foam stability, the critical micelle concentration were determined by plate method and conductivity method, has lower critical micelle concentration that is 0.13 mM. The determination results and fluorescence spectra and UV vis spectra results using.2, two Pro type calixarene surfactant TTCC as protective agent, zinc nitrate as source of zinc, ammonia as complexing agent, through simple atmospheric pressure ZnO microspheres morphology and uniform size by reflux method, the diameter of 800-1000 in the range of nm is composed of 20-30 nanoparticles of nm induced by TTCC in the assembled XRD characterization of.ZnO microspheres in the sample of six angle wurtzite structure, and the influence of different reaction conditions on the morphology and the sample size. The study found that the calcined white ZnO with mesoporous structure, the synthesis process of TTCC surfactants in samples not only plays a role in regulating the morphology of nano materials, is also involved in the skeleton. The results were obtained for SEM, TEM, TG and FT-IR verification by methyl violet solution as a model. Reaction to evaluate the photocatalytic activity of ZnO. The results showed that after 800 ZnO of calcined METHYLVIOLET dye showed good photocatalytic effect of.3, using two Pro type calixarene hexyl resorcinol calix [4] arene (TTO) induced by zinc nitrate As zinc source, ammonia as complexing agent, also used the simple reflux method was prepared by morphology and size are flower like ZnO micro nano structure, through the SEM TEM, the flower diameter of ZnO is about 1 m by petal length 500 nm, width of nano sheet composed of 200 nm.XRD results the samples have six angle wurtzite structure, and is along the (002) crystal growth, and the results are verified by results of.TG HR-TEM showed that TTO photo synthesis process in the flower like ZnO not only plays a role of inducing good, at the same time and ZnO may form a force adsorbed on its surface the results obtained showed pink, contact angle measurement results support. Then to investigate the effects of different dosage of TTO and zinc nitrate ZnO flower like morphology and size. The optical properties of FT-IR and UVDRS on flower ZnO test results show that the flower like ZnO can not only absorb ultraviolet light, at the same time Can absorb visible light. Exhibit high catalytic activity in the photodegradation experiment of methyl violet dyes, UV irradiation for 18 min, the decolorization rate can reach 96.6%, visible light irradiation of 270 min, a decoloration rate of 67.9%. metal oxide semiconductor photocatalytic degradation of dye and its main defects, then use Raman, for their defects characterization of PL and XPS, the results showed that oxygen vacancy flower like ZnO has higher concentration.

【學位授予單位】：揚州大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O643.36;TQ132.41

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