银基纳米复合材料SERS基底的制备及其对有机染料分子检测的研究
发布时间：2019-03-23 20:27
【摘要】：环境中有毒、有害物质的快速灵敏检测对于保障生命健康,维护生态安全具有重要的现实意义。结晶紫(CV)、孔雀石绿(MG)、罗丹明6G(R6G)、亚甲基蓝(MB)等都是芳香染料分子,具有高致癌性、高毒性、高残留性和致畸性等缺点,因此检测环境中这类芳香类染料分子变得至关重要。表面增强拉曼散射(SERS)光谱具有高灵敏性、高选择性和对检测样品无苛刻性要求的优点,已广泛应用于环境中检测污染物分子。在SERS研究中如何制备高效的增强基底是主要的研究方向。因此,本论文中我们以SERS为检测手段,制备了三种不同的SERS基底用于环境中高灵敏检测染料分子。主要研究内容如下:工作一:利用简单的湿化学法制备多刺状的金@银和银@金@银纳米结构作为高活性的SERS基底。使用不同形貌的银纳米结构(纳米球、纳米棒和纳米片)作为前躯体合成多刺状金@银和银@金@银纳米结构,即合成具有不同刺状表面的两种纳米材料。这些刺状结构在可见光区域具有较宽较强的吸收峰且具有较高的SERS活性。我们用CV作为探针分子,各种不同形貌的刺状银@金@银复合物比相应的金@银结构所得SERS信号大大提高。在这些纳米材料中,刺状的银@金@银纳米球具有最强的增强活性。并且该合成方法具有成本低廉、操作简单和产率高等优点,所得产物在其他领域可具有很好的应用前景。工作二:制备了一种新型的SERS活性纳米材料,即在还原石墨烯-银(rGO-Ag)复合物表面包裹上一层薄薄的聚多巴胺(PDA)作为高效的SERS基底用于染料分子的检测。在制得的还原石墨烯-银@多巴胺(rGO-Ag@PDA)复合物中,rGO-Ag是通过还原柠檬酸钠一步法制得而包裹的聚多巴胺是通过多巴胺自聚集所得到。由于包裹了一层聚多巴胺分子,使得所合成的rGO-Ag@PDA复合物对染料分子具有更强的吸附能力,因此比rGO-Ag所得到的SERS信号更强。制备的rGO-Ag@PDA复合物作为SERS基底实现了对CV、MG和MB染料分子的高灵敏检测。此外,该复合物基底相比rGO-Ag具有较高的稳定性和再循环使用能力。工作三:在一种三维大孔基底上生长银纳米片作为SERS基底实现了对小分子的检测。以三聚氰胺泡沫碳化后得到的三维大孔碳为骨架,生长聚苯胺作为还原剂,加入丁二酸控制银片的生长形貌,得到负载在三维大孔骨架上纵横交错的银纳米片(AgNSs),简称AgNSs@PANI/3D-CF杂化物。引入丁二酸,控制银片生长时间是制得纵横交错的银纳米片结构的关键因素。由于该材料具有比表面积大的优点对染料分子的吸附能力较高,且在其表面生长上纵横交错的银纳米片为该基底材料提供大量的“热点”,有效提高其SERS增强活性。AgNSs@PANI/3D-CF作为SERS基底对4-巯基苯甲酸(4-MBA)、尼罗蓝(NB)和MB等染料分子具有高灵敏检测。以NB作为探针分子也可实现对实际水样的检测。AgNSs@PANI/3D-CF因具有其独特的结构、高的拉曼增强性能和良好的重现性,在环境监测和光学传感等其它领域具有好的应用前景。
[Abstract]:The rapid and sensitive detection of toxic and harmful substances in the environment is of great practical significance for guaranteeing the health of the life and maintaining the ecological safety. Crystal violet (CV), malachite green (MG), rhodamine 6G (R6G), methylene blue (MB), and the like are aromatic dye molecules, and have the disadvantages of high carcinogenicity, high toxicity, high residue and teratogenicity, and therefore, the detection environment of such aromatic dye molecules becomes critical. The surface-enhanced Raman scattering (SERS) spectrum has the advantages of high sensitivity, high selectivity and no harsh requirements for detecting samples, and has been widely applied to the detection of contaminant molecules in the environment. In the SERS study, how to make a high-efficient substrate is the main research direction. In this paper, we use SERS as the detection means to prepare three different SERS substrates for highly sensitive detection of dye molecules in the environment. The main contents of this study are as follows: Working 1: Using a simple wet chemical method to prepare the multi-spiny gold @ silver and silver @ gold @ silver nanostructures as a highly active SERS substrate. The silver nano-structures (nanospheres, nanorods and nanosheets) with different shapes are used as the precursor to synthesize the multi-spiny gold @ silver and the silver @ gold @ silver nano-structure, namely, the two nano materials with different spiny surfaces are synthesized. These spiny structures have a relatively wide absorption peak in the visible region and have a higher SERS activity. We use the CV as the probe molecule, and the various shapes of the spiny silver @ gold @ silver complex are greatly improved than the SERS signal obtained by the corresponding gold @ silver structure. In these nano-materials, the spiny silver @ gold @ silver nanosphere has the strongest enhancement activity. And the synthesis method has the advantages of low cost, simple operation, high yield and the like, and the obtained product can have good application prospect in other fields. Work 2: a novel SERS-active nano-material is prepared, namely a thin layer of polydopamine (PDA) is coated on the surface of the reduced graphene-silver (rGO-Ag) composite as a high-efficiency SERS substrate for detection of dye molecules. In the prepared reduced graphene-silver @ dopamine (rGO-Ag@PDA) complex, rGO-Ag is obtained by the reduction of sodium citrate by one step, and the wrapped polydopamine is obtained by the self-aggregation of dopamine. Due to the inclusion of a layer of polydopamine molecules, the synthesized rGO-Ag@PDA complex has stronger adsorption capacity to the dye molecules, and therefore the SERS signal obtained by the rGO-Ag is stronger. The prepared rGO-Ag@PDA compound is used as a SERS substrate to realize high-sensitivity detection of the dye molecules of the CV, the MG and the MB. In addition, the composite substrate has a higher stability and recycling ability than the rGO-Ag. The method comprises the following steps of: growing a silver nanosheet on a three-dimensional macroporous substrate as a SERS substrate to realize the detection of small molecules. The three-dimensional macroporous carbon obtained after the carbonization of the melamine foam is taken as a framework, a polyaniline is added as a reducing agent, and a succinic acid is added to control the growth and the appearance of the silver sheet to obtain a silver nano-sheet (AgNs), which is supported on the three-dimensional macroporous framework, and is simply referred to as a AgNSs@PANI/ 3D-CF hybrid. Introducing succinic acid and controlling the growth time of the silver film is a key factor for preparing the criss-cross silver nano-sheet structure. since the material has the advantage that the specific surface area is large, the adsorption capacity of the dye molecules is high, and a plurality of "hot spot" are provided for the base material by a criss-cross silver nano sheet on the surface of the material, The SERS-enhanced active .AgNSs@PANI/ 3D-CF can be effectively improved as SERS substrate, and the dye molecules such as 4-base benzoic acid (4-MBA), indigo blue (NB) and MB have high sensitivity detection. The detection .AgNSs@PANI/ 3D-CF of the actual water sample can be realized by using the NB as the probe molecule, and has good application prospect in other fields such as environmental monitoring and optical sensing because of its unique structure, high Raman enhancement performance and good reproducibility.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X830;O657.37
本文编号：2446200
[Abstract]:The rapid and sensitive detection of toxic and harmful substances in the environment is of great practical significance for guaranteeing the health of the life and maintaining the ecological safety. Crystal violet (CV), malachite green (MG), rhodamine 6G (R6G), methylene blue (MB), and the like are aromatic dye molecules, and have the disadvantages of high carcinogenicity, high toxicity, high residue and teratogenicity, and therefore, the detection environment of such aromatic dye molecules becomes critical. The surface-enhanced Raman scattering (SERS) spectrum has the advantages of high sensitivity, high selectivity and no harsh requirements for detecting samples, and has been widely applied to the detection of contaminant molecules in the environment. In the SERS study, how to make a high-efficient substrate is the main research direction. In this paper, we use SERS as the detection means to prepare three different SERS substrates for highly sensitive detection of dye molecules in the environment. The main contents of this study are as follows: Working 1: Using a simple wet chemical method to prepare the multi-spiny gold @ silver and silver @ gold @ silver nanostructures as a highly active SERS substrate. The silver nano-structures (nanospheres, nanorods and nanosheets) with different shapes are used as the precursor to synthesize the multi-spiny gold @ silver and the silver @ gold @ silver nano-structure, namely, the two nano materials with different spiny surfaces are synthesized. These spiny structures have a relatively wide absorption peak in the visible region and have a higher SERS activity. We use the CV as the probe molecule, and the various shapes of the spiny silver @ gold @ silver complex are greatly improved than the SERS signal obtained by the corresponding gold @ silver structure. In these nano-materials, the spiny silver @ gold @ silver nanosphere has the strongest enhancement activity. And the synthesis method has the advantages of low cost, simple operation, high yield and the like, and the obtained product can have good application prospect in other fields. Work 2: a novel SERS-active nano-material is prepared, namely a thin layer of polydopamine (PDA) is coated on the surface of the reduced graphene-silver (rGO-Ag) composite as a high-efficiency SERS substrate for detection of dye molecules. In the prepared reduced graphene-silver @ dopamine (rGO-Ag@PDA) complex, rGO-Ag is obtained by the reduction of sodium citrate by one step, and the wrapped polydopamine is obtained by the self-aggregation of dopamine. Due to the inclusion of a layer of polydopamine molecules, the synthesized rGO-Ag@PDA complex has stronger adsorption capacity to the dye molecules, and therefore the SERS signal obtained by the rGO-Ag is stronger. The prepared rGO-Ag@PDA compound is used as a SERS substrate to realize high-sensitivity detection of the dye molecules of the CV, the MG and the MB. In addition, the composite substrate has a higher stability and recycling ability than the rGO-Ag. The method comprises the following steps of: growing a silver nanosheet on a three-dimensional macroporous substrate as a SERS substrate to realize the detection of small molecules. The three-dimensional macroporous carbon obtained after the carbonization of the melamine foam is taken as a framework, a polyaniline is added as a reducing agent, and a succinic acid is added to control the growth and the appearance of the silver sheet to obtain a silver nano-sheet (AgNs), which is supported on the three-dimensional macroporous framework, and is simply referred to as a AgNSs@PANI/ 3D-CF hybrid. Introducing succinic acid and controlling the growth time of the silver film is a key factor for preparing the criss-cross silver nano-sheet structure. since the material has the advantage that the specific surface area is large, the adsorption capacity of the dye molecules is high, and a plurality of "hot spot" are provided for the base material by a criss-cross silver nano sheet on the surface of the material, The SERS-enhanced active .AgNSs@PANI/ 3D-CF can be effectively improved as SERS substrate, and the dye molecules such as 4-base benzoic acid (4-MBA), indigo blue (NB) and MB have high sensitivity detection. The detection .AgNSs@PANI/ 3D-CF of the actual water sample can be realized by using the NB as the probe molecule, and has good application prospect in other fields such as environmental monitoring and optical sensing because of its unique structure, high Raman enhancement performance and good reproducibility.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X830;O657.37
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