几种无机纳米复合材料的制备及其在荧光/电化学传感器中的应用

【作者】 张艳琼；

【导师】 李灿鹏；

【作者基本信息】 云南大学 ， 分析化学， 2017， 硕士

【摘要】 电化学和荧光两种传感器,是目前被公认和应用范围较广的定量和定性分析检测技术。其与之前传统的分析检测技术相比,有很突出的优越性能,如样品用量少,检测线性范围可控、设备操作简便、成本低、仪器微型便于携带、选择性好、灵敏度高。本文分别通过采用水热法、加热回流法和常温还原法来制备了四种无机纳米复合材料,将合成得到的四种无机纳米复合材料一方面用来构建电化学传感器检测爆炸物三硝基甲苯和食品中的亚硝酸钠;另一方面用来构建荧光传感器检测具有抗氧化性、抗炎和抗疾的虾青素;再一方面用来催化氧化乙醇、甲醇和催化降解对硝基苯酚、邻硝基苯酚和亚甲基蓝。本论文主要研究内容如下:(1)通过采用温和的水热法合成柱[6]芳烃-石墨烯(CP6-Gra)纳米复合材料,利用CP6具有较大的内部空腔的优势,其可以让小分子进入其内部,构建了简单、快速、高选择性的电化学传感器来定量检测2,4,6-三硝基甲苯(TNT),检测的线性范围为:2.64-44.0 μM和44.0-132.μM,检出限为0.88 μM,该方法在检测实际样品自来水、超纯水时回收率在94.7%与101.2%之间。(2)通过采用加热回流的方法合成了钯粒子-二氧化锰(Pd-MnO2-nanoflakes)复合材料,利用亚硝酸钠在电化学上有电信号,构建了简单、高选择性的电化学传感器来定量检测亚硝酸钠,检测的线性范围为:1.0-2000.0 μM,检出限为0.33 μM,该方法在检测实际样品香肠、韩国辣白菜时回收率在83.1%与98.3%之间。此外,还用此材料来催化降解染料亚甲基蓝(MB)和环境有害物对硝基苯酚(4-NP)。(3)通过采用常温还原的方法合成铂钯粒子-碳化硅(PdPt/SiC)复合材料,利用Pd与Pt二元金属强的催化性能,构建了一种简单、快速、高选择性的电化学传感器来对乙醇和甲醇进行催化氧化。此外,还用此材料来催化降解环境有害物邻硝基苯酚(2-NP)和对硝基苯酚。(4)通过采用水热的方法合成二硫桥联β-环糊精-石墨烯(SS-β-CD-Gra)复合材料,基于主客体分子竞争识别原理,构建了一种简单、高选择性的荧光传感器对虾青素进行定量检测,检测的线性范围为:2.0-20.0 μM和20.0-40.0 μM,检出限为0.667 μM。该方法用于血清和雨生红球藻样品的检测回收率在92%与103.9%之间。更多还原

【Abstract】 The electrochemical and fluorescent sensors have been widely applied in quantitative and qualitative analysis.Compared with traditional analytical technology,electrochemical sensors and fluorescent sensors also have some advantages,such as fast detection,low sample consumption and detection of linear range controllable,equipment easy operation,low cost,micro portable instrument,good selectivity,high sensitivity.In this work,we synthesized the four kinds of inorganic nanocomposites using hydrothermal method,heating reflux method and normal temperature reduction process.The synthesis of four kinds of inorganic nanocomposite material,first,in order to build electrochemical sensor detecting explosives TNT and sodium nitrite in food,second,it was used to build the fluorescent sensors that has the oxidation resistance,anti-inflammatory and resistance to disease of Astaxanthin,third,it was used in catalytic oxidation of ethanol,methanol and catalytic degradation of p-nitrophenol,o-nitrophenol and methylene blue.The main research contents of this paper are as follows:(1)CP6-Gra nanocomposites were prepared by hydrothermal method.A electrochemical sensor has been developed for quantitative detection of TNT based on column[6]arene larger internal cavity,letting the small molecules to enter the inside.This method also have some advantages,such as simple,rapid and high selectivity.the linear range of the electrochemical sensor detect TNT:0.6-10.0 ppm and 10.0-30.0 ppm,a detection limit of 0.2 ppm.the method also used to detecting the actual samples of tap water,ultrapure water recovery rate between 94.7%and 101.2%.(2)Pd-MnO2-nanoflakes nanocomposites were prepared by heating reflux method.A electrochemical sensor towards sodium nitrite has been developed based on sodium nitrite in electrochemical signals.This method also have some advantages,such as simple and high selectivity.The electrochemical sensor of the linear range of detecting sodium nitrite:1.0-2000.0 μM,a detection limit of 0.33 μM.The method also used to detecting the actual samples of sausage,South Korea hot cabbage recovery rate between 83.1%and 98.3%.In addition,this material also use to the catalytic degradation of methylene blue dye and environmental hazards of p-nitrophenol.(3)PdPt-SiC nanocomposites were prepared by normal temperature reduction process.A electrochemical sensor towards catalytic oxidation of ethanol and methanol has been developed based on Pd and Pt dual metal catalytic properties.This method also have some advantages,such as simple,rapid and high selectivity.In addition,this material also used to the catalytic degradation of environmental pests p-nitrophenol and o-nitrophenol.(4)SS-β-CD-Gra nanocomposites were prepared by hydrothermal method.A fluorescence sensor towards astaxanthin detection has been developed based on competitive host-guest interaction.This method also have some advantages,such as sensitive,simple,fast detection and high selectivity.The fluorescence sensor of the linear range of detecting astaxanthin:0.0-20.0 μM and 20.0-40.0 μM,a detection limit of 0.667 μM.the method also is used to detecte the actual samples of serum and rain raw red recovery rate between 92.0%and 103.9%.更多还原