两亲型杯芳烃合成及其对ZnO微纳结构调控研究

发布时间：2018-01-02 18:24

本文关键词：两亲型杯芳烃合成及其对ZnO微纳结构调控研究　出处：《扬州大学》2016年硕士论文　论文类型：学位论文

【摘要】：杯芳烃作为超分子主体化合物,其独特的空腔大环结构,为众多化学研究提供了有利环境而备受瞩目。近年来,间苯二酚杯芳烃因其合成简单,优异的物理和化学性质,并且通过两亲功能修饰,其在分子识别、荧光探针、药物包埋、自组装有序组合体以及纳米材料合成方面具有显著应用。而功能化修饰后的杯芳烃可以作为保护剂和诱导剂调控不同形貌和尺寸的微纳材料的制备,则是一个极为有意义的探索,将为微纳材料的调控提供新思路、新方法,是值得研究的课题。本文从胶体与界面化学的原理出发,合成了一种新颖的两亲型杯芳烃型表面活性剂,对其理化性质进行了表征与分析,并成功将其运用于调控ZnO微纳材料的制备中,实现了球状ZnO和花状ZnO的合成,并对形成机理、理化性质以及光催化应用等方面进行了应用研究。在球状ZnO微纳材料的调控和性质研究实验中,主要讨论了反应条件对形貌的影响,并重点考察了其形成机理,接着对其光催化性能进行分析,提出催化机制；在花状ZnO的调控制备中,重点探讨了硝酸锌和表面活性剂的用量对形貌和尺寸的影响,接着对其光催化降解甲基紫溶液进行研究,对其表现出较好催化性进行了重点分析,提出催化机制。实验中制备的微纳材料形貌及结构性质分别通过SEM、TEM、XRD、TG、FT-IR等测试手段进行表征和分析。本文的主要研究内容如下：1、本文首先以间苯二酚为原料,参照文献方法合成了间苯二酚杯[4]芳烃,再在杯芳烃C-2位置上引入醛基,接着与丙二酸二甲酯反应,并水解获得了目标产物间苯二酚杯[4]芳烃羧酸(TTCC),利用核磁共振、红外等手段对产物进行了表征,同时对其水溶液进行了研究。通过起泡和稳泡性能测试结果,我们发现,TTCC表面活性剂具有很好的起泡和稳泡性能,利用吊片法和电导率法对其临界胶束浓度进行了测定,具有较低的临界胶束浓度,为0.13 mM,测定结果与荧光光谱以及紫外可见光谱结果一致。2、利用两亲型杯芳烃TTCC表面活性剂为保护剂,硝酸锌为锌源,氨水为络合剂,通过简单常压回流的方法制备了形貌和尺寸均一的ZnO微球,其直径在800-1000 nm范围内,是由20-30 nm的纳米颗粒在TTCC的诱导下组装而成。ZnO微球的XRD表征该样品为六角纤锌矿结构,并考察了不同反应条件对样品形貌和尺寸的影响。研究发现,煅烧后的白色ZnO具有介孔结构,TTCC表面活性剂在样品的合成过程中不仅起到了调控纳米材料的形貌作用,同时还参与其骨架组成,结果分别得到了SEM、TEM、TG以及FT-IR等验证。采用甲基紫水溶液为模型反应,评价了ZnO的光催化活性。结果表明,800℃煅烧前后的ZnO对甲基紫染料均表现出很好的光催化效果。3、利用两亲型杯芳烃间苯二酚己基杯[4]芳烃(TTO)为诱导剂,硝酸锌为锌源,氨水为络合剂,同样利用简单回流方法制备出了形貌和尺寸均一花状ZnO微纳结构,通过SEM、TEM可知花状ZnO的粒径约为1μm,花瓣是由长度500 nm,宽为200 nm的纳米片组成。XRD结果显示合成的样品具有六角纤锌矿结构,且是沿着(002)晶面生长,其结果也得到了HR-TEM照片的验证。TG结果表明TTO在花状ZnO的合成过程中不仅起到了很好的诱导作用,同时可能与ZnO形成某种作用力吸附在其表面而呈现粉色,结果得到了接触角测定结果的支撑。接着考察了不同TTO及硝酸锌用量对花状ZnO形貌和尺寸的影响。运用FT-IR及UVDRS对花状ZnO的光学性能进行测试,结果表明花状ZnO不仅可以吸收紫外光,同时也可吸收可见光。在对甲基紫染料的光降解实验中表现出很高的催化活性,紫外光照射18 min,脱色率可达96.6%,可见光照射270 min,脱色率可到67.9%。半导体金属氧化物光催化降解染料主要与其缺陷有关,接着运用Raman、PL以及XPS对其缺陷进行表征,结果显示花状ZnO确实具有较高浓度的氧空位。
[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.

【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36;TQ132.41

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