銀基納米復(fù)合材料SERS基底的制備及其對(duì)有機(jī)染料分子檢測(cè)的研究
發(fā)布時(shí)間：2019-03-23 20:27
【摘要】：環(huán)境中有毒、有害物質(zhì)的快速靈敏檢測(cè)對(duì)于保障生命健康,維護(hù)生態(tài)安全具有重要的現(xiàn)實(shí)意義。結(jié)晶紫(CV)、孔雀石綠(MG)、羅丹明6G(R6G)、亞甲基藍(lán)(MB)等都是芳香染料分子,具有高致癌性、高毒性、高殘留性和致畸性等缺點(diǎn),因此檢測(cè)環(huán)境中這類芳香類染料分子變得至關(guān)重要。表面增強(qiáng)拉曼散射(SERS)光譜具有高靈敏性、高選擇性和對(duì)檢測(cè)樣品無(wú)苛刻性要求的優(yōu)點(diǎn),已廣泛應(yīng)用于環(huán)境中檢測(cè)污染物分子。在SERS研究中如何制備高效的增強(qiáng)基底是主要的研究方向。因此,本論文中我們以SERS為檢測(cè)手段,制備了三種不同的SERS基底用于環(huán)境中高靈敏檢測(cè)染料分子。主要研究?jī)?nèi)容如下:工作一:利用簡(jiǎn)單的濕化學(xué)法制備多刺狀的金@銀和銀@金@銀納米結(jié)構(gòu)作為高活性的SERS基底。使用不同形貌的銀納米結(jié)構(gòu)(納米球、納米棒和納米片)作為前軀體合成多刺狀金@銀和銀@金@銀納米結(jié)構(gòu),即合成具有不同刺狀表面的兩種納米材料。這些刺狀結(jié)構(gòu)在可見(jiàn)光區(qū)域具有較寬較強(qiáng)的吸收峰且具有較高的SERS活性。我們用CV作為探針?lè)肿?各種不同形貌的刺狀銀@金@銀復(fù)合物比相應(yīng)的金@銀結(jié)構(gòu)所得SERS信號(hào)大大提高。在這些納米材料中,刺狀的銀@金@銀納米球具有最強(qiáng)的增強(qiáng)活性。并且該合成方法具有成本低廉、操作簡(jiǎn)單和產(chǎn)率高等優(yōu)點(diǎn),所得產(chǎn)物在其他領(lǐng)域可具有很好的應(yīng)用前景。工作二:制備了一種新型的SERS活性納米材料,即在還原石墨烯-銀(rGO-Ag)復(fù)合物表面包裹上一層薄薄的聚多巴胺(PDA)作為高效的SERS基底用于染料分子的檢測(cè)。在制得的還原石墨烯-銀@多巴胺(rGO-Ag@PDA)復(fù)合物中,rGO-Ag是通過(guò)還原檸檬酸鈉一步法制得而包裹的聚多巴胺是通過(guò)多巴胺自聚集所得到。由于包裹了一層聚多巴胺分子,使得所合成的rGO-Ag@PDA復(fù)合物對(duì)染料分子具有更強(qiáng)的吸附能力,因此比rGO-Ag所得到的SERS信號(hào)更強(qiáng)。制備的rGO-Ag@PDA復(fù)合物作為SERS基底實(shí)現(xiàn)了對(duì)CV、MG和MB染料分子的高靈敏檢測(cè)。此外,該復(fù)合物基底相比rGO-Ag具有較高的穩(wěn)定性和再循環(huán)使用能力。工作三:在一種三維大孔基底上生長(zhǎng)銀納米片作為SERS基底實(shí)現(xiàn)了對(duì)小分子的檢測(cè)。以三聚氰胺泡沫碳化后得到的三維大孔碳為骨架,生長(zhǎng)聚苯胺作為還原劑,加入丁二酸控制銀片的生長(zhǎng)形貌,得到負(fù)載在三維大孔骨架上縱橫交錯(cuò)的銀納米片(AgNSs),簡(jiǎn)稱AgNSs@PANI/3D-CF雜化物。引入丁二酸,控制銀片生長(zhǎng)時(shí)間是制得縱橫交錯(cuò)的銀納米片結(jié)構(gòu)的關(guān)鍵因素。由于該材料具有比表面積大的優(yōu)點(diǎn)對(duì)染料分子的吸附能力較高,且在其表面生長(zhǎng)上縱橫交錯(cuò)的銀納米片為該基底材料提供大量的“熱點(diǎn)”,有效提高其SERS增強(qiáng)活性。AgNSs@PANI/3D-CF作為SERS基底對(duì)4-巰基苯甲酸(4-MBA)、尼羅藍(lán)(NB)和MB等染料分子具有高靈敏檢測(cè)。以NB作為探針?lè)肿右部蓪?shí)現(xiàn)對(duì)實(shí)際水樣的檢測(cè)。AgNSs@PANI/3D-CF因具有其獨(dú)特的結(jié)構(gòu)、高的拉曼增強(qiáng)性能和良好的重現(xiàn)性,在環(huán)境監(jiān)測(cè)和光學(xué)傳感等其它領(lǐng)域具有好的應(yīng)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.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X830;O657.37
本文編號(hào)：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.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X830;O657.37
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