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题名: 发光铜纳米簇材料的制备及性能的研究
作者: 刘华云
答辩日期: 2014-05-26
导师: 王传义
专业: 环境工程
授予单位: 中国科学院大学
授予地点: 北京
学位: 博士
关键词: 铜纳米簇 ; 核壳结构 ; 光致发光 ; 巯基乙酸 ; 可调发光
摘要: 金属纳米簇在生物成像、化学传感、生物标记等方面具有很广的应用。其中,金、银纳米簇因优异的发光性能而被广泛研究和使用。但它们价格昂贵。铜纳米簇具有成本低,尺寸小及大的斯托克位移,有望成为金、银的替代品。然而,铜纳米簇易氧化,不稳定性的缺点。利用核-壳结构有利于保护材料中的核免于被空气氧化。本论文研究铜纳米簇的制备及其影响因素,探究铜纳米簇的结构组成及其对光学性能影响因素。具体的研究内容分为以下几个部分:(1)深入研究了铜纳米簇在水溶液中的存在形式。这与其稳定性和光、电、催化性能密切相关。研究发现纳米簇是由5个铜原子的核构成,和正一价铜与TGA配合物形成的壳,组成的核壳结构。这种结构具有很强的抗氧化能力,而且对改善光学性能具有重要意义。 2)在铜纳米簇尺寸研究中,考察TGA浓度对铜纳米簇的尺寸及光学性能影响。研究发现,TGA的浓度能够调控Cu(0)@Cu(I)-TGA核-壳材料颗粒粒径,从而改变材料的发光性能。较高浓度的TGA(pH=3)导致纳米簇颗粒间的交联和团聚(粒径75 nm);较低浓度(pH=5.8)下,由于TGA自组装层数少,核-壳材料的粒径仅为1nm左右。过大及过小粒径材料的荧光效果均不理想。相反,粒径为2.5 nm核-壳材料(pH=4)展示了良好的紫外激发荧光发光性能。 3)在此基础上还研究了不加还原剂水合肼,采用超声处理TGA的铜盐溶液所形成的铜纳米簇。研究发现,超声处理能够增强TGA的还原能力,以致同样形成了Cu0@Cu+-TGA核-壳材料。pH=2.4、pH=3铜纳米簇的溶液具有荧光,并且pH=3的溶液荧光较强,而pH=4的溶液没有荧光。其中主要的原因在于TGA的超声还原作用,有效地控制了粒子的粒径,从而影响其光学性能。
4)研究了不同配体及pH值对铜纳米簇的形成及光学性能的影响研究。一方面,通过三辛基甲基氯化铵和十六烷基三甲基溴化铵的交替使用,能够有效改变铜纳米簇的发光性能,产生不同颜色的铜纳米簇。另一方面,巯基乙酸和三乙烯四胺对溶液pH值的调节能够影响铜纳米簇的发光性能。发射波长随pH值增大而红移、量子产率随pH值增大先增大再减小再增大。发射强度也能够随着溶液的浓度减小而增大。这些结果均是首次发现的。在此基础上,铜纳米簇在生物成像中的应用研究。通过大肠杆菌作为参考对象,考察铜纳米簇在生物成像方面的实际运用,发现铜纳米簇,毒性较低,能有效提高大肠杆菌的光学成像能力。
英文摘要:
ABSTRACT Cu nanoclusters are more advantageous over other noble metals in size and stock shifts, and promising to be candidates in the place of Au and Ag. Cu nanoclusters are significant in bioimagining,chemical sensing,biolabeling.However, application of Cu nanoclustrs is limited to their unstability and prone to oxidation. There are still a few challenges in preparation and properties of Cu nanoclusters. In the paper, we investigated preparation and influence of properties, and relations of optical properties. 1) It is important to understand existing form of Cu nanoclusters. On one hand, existing form of Cu nanoclusters is related to their stability. On the other hand, optical, electrical, catalytical properties could be influence by their existing form. In our experiment, we found Cu nanoclusters consisted of core of 5 copper atoms and large shell of Cu-TGA, who were able to antioxidate in air and improve optical properties. 2) ligands are important to form metal nanoclusters. In the experiments, LSPR was toward blueshift when concentration of TGA was increased. QYs were changed with increase of TGA concentration. These changes resulted from TGA functions. 3) We discussed the relation between ultrasonic treatment of thiol copper and optical properties. There was no fluorescent phenomena under too high or too low pH value. There were several hundreds nanometers particles without LSPR and fluorescence phenomena in solution contained at pH=3, few nanometers particles and LSPR without fluorescence phenomena at pH=5.8, fluorescence phenomena at pH=4 . 4) Photoemission properties have been investigated in the paper,first,tricaprylmethylammonium chloride and Hexadecyl trimethyl ammonium Bromide was used respectively as surfactants, and emission wavelength of Cu nanoclusters was different. Second, optical properties of Cu nanoclusters were changed because of adjustment of pH value, emission wavelength, quantum dot yields etc. emission intensity was related with concentration of Cu nanoclusters. Application of Cu nanoclusters has also been studied using E. coli ATCC 25922 cells in bioimagining.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3412
Appears in Collections:环境科学与技术研究室_学位论文

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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
刘华云. 发光铜纳米簇材料的制备及性能的研究[D]. 北京. 中国科学院大学. 2014.
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