新颖多孔复合SERS基底的制备及性能的研究
发布时间：2018-11-06 07:50
【摘要】：具有广阔应用前景的表面增强拉曼散射(SERS)以其较高的灵敏度和较好的分辨率在光谱材料等领域引起了热切的关注。众所周知,SERS技术的持续发展主要依赖于新型SERS活性基底的研究和制备。只有新颖多功能的SERS基底发展起来,才能完美地解决活性SERS基底匮乏的难题,达到增加拉曼光谱应用性的目的。构建均一、有效的SERS基底仍然具有挑战性,因为这一般都需要高成本的消耗和复杂的合成过程。为了解决上述问题,本文首先采用溶剂热法制备了多孔花状的羟基磷灰石/Ag复合物作为基底,讨论了SERS增强性能和催化还原对硝基苯酚的能力。另外我们还通过溶胶凝胶法制备了多孔有序的Ni掺杂的TiO2反蛋白石光子晶体和Co离子掺杂的GO-TiO2反蛋白石光子晶体,主要讨论了其SERS性能及光电转化、光催化性能。论文主要研究结果如下：1.通过溶剂热一锅法制备了多孔的HA/Ag纳米复合物,并利用XRD、SEM、 BET、Raman等技术对产物进行表征。结果表明,大小相对均匀的Ag纳米颗粒附着在多孔花状的HA表面上,多孔HA/Ag纳米复合物可以用作表面增强拉曼光谱(SERS)基底,对罗丹明6G(Rh6G)的拉曼光谱有很好的增强作用,检测Rh6G极限达到10-10。另外,上述产物能够8 min内催化还原对硝基苯酚(4-NP)。本实验简单、方便的合成方法也为制备其他多功能的复合材料提供了借鉴。2.以我们以均匀大小的PS球为模板,制备出了有序多孔的反蛋白石结构的Ni掺杂的TiO2光子晶体,并将其有效的运用于活性SERS基底。结果表明,掺杂的Ni离子能进入TiO2的晶格,在纳米TiO2的带隙中形成丰富的掺杂能级,显著提高了反蛋白石结构TiO2的SERS性能。所以该基底的拉曼光谱对4-巯基苯甲酸(4-MBA)具有有很好的检测效果,检测极限达到10-11。另外,在模拟太阳光照射下,90min对亚甲基蓝(MB)的光催化降解率可达95%。因此,该反蛋白石薄膜有望在污水的检测、环境清洁等方面得到应用。3.在前期研究的基础上,通过多步法合成多孔有序的反蛋白石结构的Co离子掺杂的GO-TiO2光子晶体,并将其作为表面增强拉曼散射(SERS)的活性基底。研究了Co的掺杂和GO的存在对于所制备的光子晶体SERS基底性能的改进。结果表明,适量的Co掺杂能够在反蛋白石TiO2的能隙中靠近导带的位置形成掺杂能级,促进电荷转移的过程；适量GO的加入也能起到增强Raman的作用,进而显著地提高了GO复合Co-TiO2基底对4-巯基苯甲酸(4-MBA)拉曼光谱的增强能力,进而提高了SERS性能,检测4-MBA极限达到10-12。另外,该反蛋白石薄膜在模拟太阳光的照射下光催化MB降解的效率和光电流密度是普通的反蛋白石TiO2薄膜1.5倍和6倍。
[Abstract]:Surface enhanced Raman scattering (SERS), which has wide application prospects, has attracted much attention in the field of spectral materials due to its high sensitivity and good resolution. As we all know, the sustainable development of SERS technology mainly depends on the research and preparation of new active substrates of SERS. Only when novel multifunctional SERS substrates are developed can the problem of lacking active SERS substrates be solved perfectly and the application of Raman spectra be increased. Building a uniform and effective SERS substrate remains challenging because it typically requires high cost and complex composition processes. In order to solve the above problems, the porous flower-like hydroxyapatite / Ag composites were prepared by solvothermal method. The enhancement of SERS and the ability of catalytic reduction of p-nitrophenol were discussed. In addition, porous ordered TiO2 opal photonic crystals doped with Ni and GO-TiO2 opal photonic crystals doped with Co ion were prepared by sol-gel method. The properties of SERS, photoconversion and photocatalysis were discussed. The main research results are as follows: 1. Porous HA/Ag nanocomposites were prepared by solvothermal one-pot method and characterized by XRD,SEM, BET,Raman. The results showed that the Ag nanoparticles with relatively uniform size were attached to the porous HA surface, and the porous HA/Ag nanocomposites could be used as (SERS) substrates for enhanced Raman spectra. The Raman spectra of Rhodamine 6G (Rh6G) were enhanced and the detection limit of Rh6G was 10-10. In addition, the above products can catalyze the reduction of p-nitrophenol (4-NP) in 8 min. This experiment is simple and convenient for the preparation of other multifunctional composite materials. 2. An ordered porous Ni doped TiO2 photonic crystal was prepared by using a uniform size PS sphere as a template and was effectively applied to the active SERS substrate. The results show that the doped Ni ions can enter the lattice of TiO2 and form rich doped energy levels in the band gap of TiO2 nanocrystalline, which improves the SERS performance of TiO2 with inverse opal structure. Therefore, the Raman spectrum of the substrate has a good effect on the detection of 4-mercaptobenzoic acid (4-MBA), and the detection limit is up to 10-11. In addition, under simulated solar irradiation, the photocatalytic degradation rate of methylene blue (MB) by 90min was up to 95. Therefore, the reverse opal film is expected to be used in the detection of sewage, environmental cleanliness and other aspects. On the basis of previous studies, GO-TiO2 photonic crystals doped with Co ions with porous and ordered antiopal structure were synthesized by multistep method and used as active substrates for surface-enhanced Raman scattering (SERS). The improvement of the properties of the photonic crystal SERS substrate prepared by doping Co and the existence of GO has been studied. The results show that the doping level can be formed near the conduction band in the energy gap of opal TiO2 by proper amount of Co doping, which can promote the process of charge transfer. The addition of appropriate amount of GO can also enhance the Raman, thus significantly improving the enhancement of the Raman spectra of 4-mercaptobenzoic acid (4-MBA) on the GO composite Co-TiO2 substrate, and further improving the SERS performance. The detection limit of 4-MBA is 10-12. In addition, the photocatalytic MB degradation efficiency and photocurrent density of this opal film are 1.5 and 6 times higher than those of conventional opal TiO2 films under simulated solar irradiation.
【学位授予单位】：安徽大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O657.37;TB33
本文编号：2313623
[Abstract]:Surface enhanced Raman scattering (SERS), which has wide application prospects, has attracted much attention in the field of spectral materials due to its high sensitivity and good resolution. As we all know, the sustainable development of SERS technology mainly depends on the research and preparation of new active substrates of SERS. Only when novel multifunctional SERS substrates are developed can the problem of lacking active SERS substrates be solved perfectly and the application of Raman spectra be increased. Building a uniform and effective SERS substrate remains challenging because it typically requires high cost and complex composition processes. In order to solve the above problems, the porous flower-like hydroxyapatite / Ag composites were prepared by solvothermal method. The enhancement of SERS and the ability of catalytic reduction of p-nitrophenol were discussed. In addition, porous ordered TiO2 opal photonic crystals doped with Ni and GO-TiO2 opal photonic crystals doped with Co ion were prepared by sol-gel method. The properties of SERS, photoconversion and photocatalysis were discussed. The main research results are as follows: 1. Porous HA/Ag nanocomposites were prepared by solvothermal one-pot method and characterized by XRD,SEM, BET,Raman. The results showed that the Ag nanoparticles with relatively uniform size were attached to the porous HA surface, and the porous HA/Ag nanocomposites could be used as (SERS) substrates for enhanced Raman spectra. The Raman spectra of Rhodamine 6G (Rh6G) were enhanced and the detection limit of Rh6G was 10-10. In addition, the above products can catalyze the reduction of p-nitrophenol (4-NP) in 8 min. This experiment is simple and convenient for the preparation of other multifunctional composite materials. 2. An ordered porous Ni doped TiO2 photonic crystal was prepared by using a uniform size PS sphere as a template and was effectively applied to the active SERS substrate. The results show that the doped Ni ions can enter the lattice of TiO2 and form rich doped energy levels in the band gap of TiO2 nanocrystalline, which improves the SERS performance of TiO2 with inverse opal structure. Therefore, the Raman spectrum of the substrate has a good effect on the detection of 4-mercaptobenzoic acid (4-MBA), and the detection limit is up to 10-11. In addition, under simulated solar irradiation, the photocatalytic degradation rate of methylene blue (MB) by 90min was up to 95. Therefore, the reverse opal film is expected to be used in the detection of sewage, environmental cleanliness and other aspects. On the basis of previous studies, GO-TiO2 photonic crystals doped with Co ions with porous and ordered antiopal structure were synthesized by multistep method and used as active substrates for surface-enhanced Raman scattering (SERS). The improvement of the properties of the photonic crystal SERS substrate prepared by doping Co and the existence of GO has been studied. The results show that the doping level can be formed near the conduction band in the energy gap of opal TiO2 by proper amount of Co doping, which can promote the process of charge transfer. The addition of appropriate amount of GO can also enhance the Raman, thus significantly improving the enhancement of the Raman spectra of 4-mercaptobenzoic acid (4-MBA) on the GO composite Co-TiO2 substrate, and further improving the SERS performance. The detection limit of 4-MBA is 10-12. In addition, the photocatalytic MB degradation efficiency and photocurrent density of this opal film are 1.5 and 6 times higher than those of conventional opal TiO2 films under simulated solar irradiation.
【学位授予单位】：安徽大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O657.37;TB33
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