石墨烯量子点—离子液体复合物的制备、性能研究及其在阴离子检测中的应用

发布时间：2018-01-14 18:04

本文关键词：石墨烯量子点—离子液体复合物的制备、性能研究及其在阴离子检测中的应用　出处：《浙江理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：部分阴离子对生态环境和人体健康具有危害。发展简单、快速、准确的阴离子直接检测方法具有重要的实际应用价值。荧光传感分析检测快速、灵敏,是当前的研究热点。石墨烯量子点(graphene quantum dots,GQDs)作为新型纳米荧光碳材料,除具有明显的量子限域效应和边界效应外,还具有易于合成、毒性低、发光稳定等优点。建立新颖的GQDs改性方法并拓展其在阴离子直接检测中的应用具有重要的意义。本论文利用具有阴离子交换功能的离子液体作为修饰剂,通过改变离子液体的结构,制备得到两种石墨烯量子点-离子液体复合材料,考察了所得复合材料对阴离子的选择性,分别实现了对两种阴离子的直接检测。主要研究内容如下:(1)论文建立了石墨烯量子点的简单制备方法并对其进行了系统的性能表征。具体为:以1,3,6-三硝基芘为碳源,在碱性NaOH水溶液中,利用水热处理过程中碳源的分子融合,制备得到富含羟基、具有良好水分散性的石墨烯量子点。利用透射电子显微镜(TEM)、X-射线光电子能谱(XPS)、原子力显微镜(AFM)、傅立叶变换红外光谱(FTIR)和荧光光谱(FL spectrum)对所得GQDs进行了性质表征。结果表明,GQDs尺寸约为2~3 nm,片层厚度约为3-5层石墨烯厚度,富含羟基基团,GQDs在365 nm紫外光照射下发射绿色荧光,最大激发波长为470 nm,最大发射波长为512 nm,且其荧光性能具有非激发波长依赖性,以罗丹明B为标准荧光参照物测得荧光量子产率为12.1%。(2)论文建立了石墨烯量子点-离子液体(1-丁基-3-甲基咪唑四氟硼酸盐,BMIMBF4)复合物(BMIMBF4-GQDs)的简单制备方法并考察了复合物在Fe(CN)63-检测中的应用。BMIMBF4-GQDs的制备方法和原理为:在超声条件下,在GQDs溶液中加入一定比例的BMIMBF4,利用石墨烯量子点与离子液体间的π-π和阳离子π作用,制备得到石墨烯量子点-离子液体复合物。利用TEM、XPS、AFM、FTIR和FL spectrum对最优条件下制备所得BMIMBF4-GQDs复合物进行了表征。与纯GQDs相比,XPS与FTIR表征结果显示复合物中出现了BMIMBF4的特征信号,AFM表征表明复合后BMIMBF4-GQDs片层厚度较GQDs增加,证明BMIMBF4在GQDs上的有效复合。GQDs与离子液体复合并未引起GQDs粒径的显著变化。BMIMBF4-GQDs复合物的荧光性质与纯GQDs类似,最大激发波长和最大发射波长均未发生显著变化。这说明BMIMBF4的引入未明显改变GQDs的荧光性质。考察了BMIMBF4-GQDs复合物的阴离子选择性,发现Fe(CN)63-可以猝灭BMIMBF4-GQDs的荧光。据此建立了BMIMBF4-GQDs直接检测Fe(CN)63-的荧光检测方法。在最优实验条件下,BMIMBF4-GQDs复合物检测Fe(CN)63-的线性范围为0.1μM-2.5 mM,检测限为0.04μM。(3)论文建立了石墨烯量子点-离子液体(1-丁基-3-甲基咪唑六氟磷酸盐,BMIMPF6)复合物(BMIMPF6-GQDs)的简单制备方法并考察了复合物在S2-检测中的应用。采用类似的合成方法,将富含羟基的GQDs与BMIMPF6复合,制备得到BMIMPF6-GQDs复合物。利用TEM、XPS、AFM、FTIR和FL spectrum对制备所得BMIMPF6-GQDs复合物进行表征,证明了BMIMPF6的成功复合,且BMIMPF6的复合未明显改变GQDs的粒径和荧光性质。考察了BMIMPF6-GQDs复合物的阴离子选择性,结果表明S2-可猝灭BMIMPF6-GQDs的荧光。依据S2-对BMIMPF6-GQDs的荧光猝灭效应,建立了BMIMPF6-GQDs直接检测S2-的荧光检测方法。BMIMPF6-GQDs复合物检测S2-的线性范围为0.01μM-0.3 mM,检测限为0.008μM。
[Abstract]:Part of anion harm to the ecological environment and human health. The development of simple, rapid and accurate method for direct detection of anions has important practical application value. The fluorescence sensing analysis assay is rapid, sensitive, is the focus of current research. The graphene quantum dots (graphene quantum, dots, GQDs) as a new type of fluorescent nano carbon materials, has obvious the quantum confinement effect and boundary effect, but also has the advantages of easy synthesis, low toxicity, stable luminescence etc. to establish novel GQDs modified method and has important significance to expand its applications in anionic direct detection. This paper using ionic liquid with anion exchange function as modifier, by changing the structure of ion the liquid, prepared two kinds of graphene quantum dots and ionic liquid composite materials, effects of composite materials on anion selective income, respectively the two kinds of Yin Direct determination of ions. The main contents are as follows: (1) this paper established a simple method for preparing graphene quantum dots and the performance characterization system. It uses 1,3,6- three nitropyrene as carbon source in alkaline aqueous solution of NaOH, molecular carbon source utilization of water during heat treatment fusion, prepared with hydroxyl group, with good dispersion of the graphene quantum dots by transmission electron microscopy (TEM), X- ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Fu Liye transform infrared spectroscopy (FTIR) and fluorescence spectra (FL spectrum) of the GQDs was characterized. The results show that the size of GQDs is about 2~3 nm, film thickness of 3-5 layer thickness of graphene, rich in hydroxyl groups, GQDs fluorescence at 365 nm under UV light irradiation, the maximum excitation wavelength is 470 nm, the maximum emission wavelength of 512 nm, and the fluorescence properties of non excitation The wavelength dependent, with Luo Danming B as reference standard fluorescence measured the fluorescence quantum yield of 12.1%. (2) this paper established the graphene quantum dots and ionic liquids (1- butyl -3- methylimidazolium tetrafluoroborate, BMIMBF4) compound (BMIMBF4-GQDs) has the advantages of simple preparation method and the effects of the compound in Fe (CN) system the preparation method and principle for the application of.BMIMBF4-GQDs 63- detection in the under ultrasonic conditions in the GQDs solution ratio of BMIMBF4, by using graphene quantum dots and ionic liquid between Pi Pi and PI cation, prepared graphene quantum dot ionic liquid composites. By using TEM, XPS. AFM, FTIR and FL spectrum on the optimum conditions of preparation of the BMIMBF4-GQDs composites were investigated. Compared with GQDs, XPS and FTIR characterization results show a characteristic signal of BMIMBF4 composite, AFM composite BMIMBF4-GQDs characterization showed that the lamellar thickness Compared with the increase of GQDs, BMIMBF4 in GQDs on the effective compound of.GQDs and ionic liquid composite did not cause the fluorescence properties of GQDs particle size change of.BMIMBF4-GQDs complex and similar to the pure GQDs, the maximum excitation wavelength and the maximum emission wavelength were not significantly changed. The fluorescence properties of the introduction of BMIMBF4 did not change significantly GQDs was studied. Anion selective BMIMBF4-GQDs complexes, Fe (CN) 63- can quench the fluorescence of BMIMBF4-GQDs. BMIMBF4-GQDs was established based on the direct detection of Fe (CN) fluorescence detection method of 63-. Under the optimum conditions, the BMIMBF4-GQDs complex detection Fe (CN) 63- in the linear range of 0.1 M-2.5 mM, the detection limit was 0.04 M. (3) this paper established the graphene quantum dots and ionic liquids (1- butyl -3- methylimidazolium six fluophosphate, BMIMPF6) compound (BMIMPF6-GQDs) has the advantages of simple preparation method and tested compound in S2- inspection The application of measurement. The synthesis method is similar to that of GQDs and BMIMPF6 will be rich in hydroxyl compound, preparation of BMIMPF6-GQDs composite. The use of TEM, XPS, AFM, FTIR and FL spectrum of the prepared BMIMPF6-GQDs composites were characterized and proved the success of the BMIMPF6 composite particle composite, GQDs and BMIMPF6 did not change significantly the size and fluorescence properties was studied. The anion selective BMIMPF6-GQDs complexes, the results showed that S2- can quench the fluorescence of BMIMPF6-GQDs. Based on the fluorescence quenching effect of S2- on BMIMPF6-GQDs, a linear range of BMIMPF6-GQDs direct detection of.BMIMPF6-GQDs fluorescence detection method for S2- complex detection of S2- 0.01 M-0.3 mM, the detection limit is 0.008 M.

【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332;O657.3

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