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1、分 类 号:_ UDC:_盲审代码:_ 密级:_硕硕 士士 学学 位位 论论 文文具有光电催化功能的有机-无机纳米杂化膜的制备及应用学科、专业 : 有机化学 研 究 方 向: 物理有机化学 完 成 日 期: 2008 3.10 IX X X X 大大 学学 学学 位位 论论 文文 独独 创创 性性 声声 明明 本人郑重声明:所呈交的学位论文是我个人在导师指导下进行的研究工作及取得的研究成果。尽我所知,除了文中特别加以标注和致谢的地方外,论文中不包含其他人已经发表或撰写过的研究成果,也不包含为获得 XX 大学或其它教育机构的学位或证书而使用过的材料。与我一同工作的同志对本研究所做的任何贡献均已在
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3、文II具有光电催化功能的有机-无机纳米杂化膜的制备及应用摘 要二维有序超薄的有机-无机杂化膜在光学、微电子学以及分子敏感元器件等方面的应用倍受人们的广泛关注, 在分子水平设计及合成具有功能性的有机-无机复合超薄膜是当代化学研究的热点和前沿课题之一。本论文利用Langmuir-Blodgett (LB) 膜技术及自组装技术,制备了一系列具有光电催化功能的有机-无机纳米超薄膜,并应用于修饰电极的制备、贵重金属纳米团簇的合成以及生物分子和手性分子的光电识别,具体的研究结果有:1. 利用LB膜技术制备出了一系列有机-无机纳米杂化膜,如clay/(phen)2(dC18-bpy)2+ (简写为Clay-
4、Ru) 和TiO2/Ru(phen)2 (dC18- bpy)2+ (简写为TiO2-Ru) (phen=1,10-phenanthro-line,dC18bpy = 4,4- dioctadecyl-2,2-bipyridyl)等。AFM观察发现沉积在玻璃等基材表面的有机-无机杂化膜具有特征的片状结构,其纳米单层杂化膜的平均厚度为3.4 0.5 nm。2. 探讨了纳米单层Clay-Ru杂化膜修饰电极的界面电子传递机理。通过研究Clay-Ru 纳米单层杂化膜修饰的ITO电极对DNA的主要成份之一,guanosine 5- monophosphate(GMP)的光电催化氧化行为,实验结果发现:(
5、a) 紧密排列于ITO电极表面的非电活性粘土的加入降低了电极的电化学活性,但有效提高了电极的稳定性和光催化氧化摘要III能力;(b) 具有供电子能力的GMP的加入,能有效提高ITO/Clay-Ru修饰电极的电子传递效率;(c) 杂化膜修饰电极的电子传递直接通过粘土纳米单层进行。3. 以纳米单层的有机-无机杂化膜 TiO2-Ru 为模板,运用光化学还原法制备出了具有光电增强特性的贵金属Pt纳米团簇,并用原子力显微镜(AFM)、x-射线光电子能谱(XPS)以及循环伏安法(CV)等进行了相应表征。4. 创造了新奇的具有立体选择性的固体表面并应用于手性分子的光电识别。运用 LB 膜技术及自组装技术,在
6、纳米单层的二氧化钛表面上,组装水溶性手性配合物分子-Os(phen)32+,创造了一种新奇的没有立体阻碍效应并具有手性分子识别能力的有机-无机杂化膜。实验发现利用上述膜修饰的 ITO 电极对 S和 R-联萘酚以及(L)和(D)-2-苄基-2-(5-氟尿嘧啶-1-基)甲基甲酰基氨基乙酸甲酯异构体分子产生显著的氧化光电流差异。上述实验结果将为研制快捷、方便、且具高灵敏度的手性分子传感器提供重要的理论和实验依据。关键词 有机无机杂化膜,修饰电极,手性识别,贵金属纳米团簇,光电催化PREPARATION AND APPLICATION OF ORGANIC-INORGANIC HYBRID NANOF
7、ILMS WITH PHOTOELCTROCATALYTIC PROPERTIESABSTRACTCreation of a functional solid surface is one of the most challenging subjects for its wide applications to optical devices, microelectronic devices and sensors. In this dissertation, a series of organic-inorganic ultrathin films have been prepared by
8、 applying the combined methods of Langmuir-Blodgett (LB) and self-assemble techniques. Such films have been used as electrode modifiers, as templates to prepare metal nanoclusters, and as electrochemical sensors for chiral molecules. Our investations are listed as follows: (1) A series of organic-in
9、organic ultrathin films, which are composed of a monolayer of metal complex such as M(phen)2(dC18bpy)2+ (M=Os or Ru, phen=1,10-phenanthroline, dC18bpy = 4,4- dioctadecyl- 2,2bipyridyl) and an inorganic monolayer film (clay and titanium dioxide) have been fabricated by LB method. Atomic force microsc
10、opy 硕士学位论文IV(AFM) shows that the single-layered hybrid film of clay/ Ru(phen)2 (dC18bpy)2+(denoted as Clay-Ru) or TiO2/Ru(phen)2(dC18bpy)2+ (denoted as TiO2-Ru) is closely packed at a surface pressure of 25 mN m-1 and have a thickness of 3.4 0.5 nm. These ultrathin films have been used as electrode
11、modifiers. When applied to oxidize the mononucleotide of guanosine 5- monophosphate (GMP), a large catalytic oxidative current is achieved on the modified electrodes at the applied potential above 700 mV (vs Ag|AgCl|KCl ) and, more significantly, this response is further enhanced under light irradia
12、tion (360nm). Moreover, it is revealed that the photocurrent density decreases with an increasing number of layers of hybrid films, indicating that the harvesting of photoexcited electrons vertically through the inorganic nanosheets is not efficient. For efficient photocurrent generation, a lateral
13、interlayer connection to all of the inorganic nanosheets with Ag paste has been used and thus a dramatic improvement in the sensitivity of photocatalytic response is obtained.(2) The TiO2-Ru hybrid film is utilized as a template to prepare Pt nanoclusters by using a photochemical reduction process.
14、The obtained TiO2-Ru-Pt hybrid film is characterized by AFM, XPS, CV and so on. Our studies demonstrate that the photocurrent is strongly enhanced by being deposited Pt nanoclusteres onto the surface of the modified electrode under light irradiation (360nm). (3) A series of chiral sensing electrods
15、have been fabricated by coating ITO elctrodes with a hybrid film of metal complex and an inorganic monolayer such as titanium dioxide and montmorillonite, respectively. By applying the combined methods of Langmuir-Blodgett (LB) and self-assembly techniques, a monolayer of a water-soluble chiral metal (Ru and Os) complex, which acts as a mediator of oxidizing a target molecule, is fixed electrostatically onto an inorganic monolayer film. Chiral sensing is demonstrated by monitoring a photocurrent