掺磷TiO_2优化TiO_2/MBA/Ag三明治结构的SERS性能

本文以磷酸为磷源,通过溶胶水热法制备磷掺杂TiO_2,利用Lee和Meisel的方法制备银溶胶,以4-巯基苯甲酸(MBA)为探针分子,通过构建TiO_2/MBA/Ag三明治结构,研究磷掺杂二氧化钛对该基底表面增强拉曼(SERS)性能的提升。通过TEM、XRD、XPS、DRS和拉曼光谱图表征二氧化钛的形貌结构、化学组成、光学和拉曼性能,结果表明,制备出的磷掺杂二氧化钛为锐钛矿型纳米颗粒,粒径范围6~12nm,XPS显示磷以P~(5+)替代了Ti~(4+),形成O-P-O键掺入TiO_2的晶格中,当磷的掺杂量在1.77%时,TiO_2/MBA/Ag三明治体系具有最佳的SERS信号,这是因为适量的磷掺杂降低了TiO_2的能带间隙,丰富TiO_2的表面态,这能促进TiO_2向MBA分子的电荷转移。     

Ag纳米颗粒的引入方式对TiO_2三维有序多孔/Ag复合结构SERS性能的影响

用PS(聚苯乙烯)微球作为模板制备出TiO_2三维多孔有序结构(TiO_2-3DOM),在此基础上,着重探究了银纳米颗粒的引入方式对整个TiO_2三维多孔/Ag复合结构SERS性能的影响。研究表明,通过银镜反应得到的TiO_2三维多孔/Ag复合结构是一种灵敏性强的基底,对罗丹明(R6G)分子的检测极限可低至10-10mol/L。     

基于g-C_3N_4/Ag/TiO_2基底上RhB的催化降解过程研究

表面增强拉曼光谱(SERS)具有无与伦比的光谱性能,因此在分析化学、催化等领域得到了广泛的关注,在适当的条件甚至可以做到单分子水平检测。SERS可以得到分子的振动能级信息,而且具有很高的灵敏度和选择性,尤其在表面、界面研究方面具有较大的优势。因此我们制备了具有较好催化性能的TiO_2,在它的表面沉积了贵金属Ag,然后再掺杂g-C_3N_4,形成g-C_3N_4/Ag/TiO_2复合催化剂。通过修饰和掺杂,催化剂的吸收从紫外区移动到可见区,同时光生载流子受到了抑制,因此材料的催化性能得到了提高。我们以RhB染料作为探针分子,用SERS研究了该分子的催化降解过程。     

TiO_2/石墨烯/Ag复合结构SERS实验

基于氧化物半导体的光催化特性,能够降解有机物分子,使表面增强拉曼散射基底得以重复使用。提出了银纳米颗粒有效修饰覆盖有石墨烯的二氧化钛纳米棒阵列(TiO_2/石墨烯/Ag)复合结构作为表面增强拉曼散射基底,并对其进行了实验研究。利用水热法制备了二氧化钛纳米棒阵列;采用湿法转移石墨烯和光照还原方法制备了TiO_2/石墨烯/Ag复合结构。用罗丹明6G(R6G)分子作为探测分子,结果表明:随着紫外光照沉积时间增加,探针分子的拉曼信号先增强后减弱;计算得到最大增强因子值约为2.6×106。此外,还对TiO_2/石墨烯/Ag复合结构的紫外自清洁特性进行了初步实验,结果表明,紫外光照射20min后,其拉曼强度下降到42.3%,具有一定的紫外清洁效果。     

Au-TiO_2纳米复合基底的制备及其SERS研究

通过溶胶-水热法合成TiO_2纳米粒子,然后采用光催化还原法通过改变氯金酸(HAuCl4)水溶液浓度和光照时间等参数制备不同量Au沉积的TiO_2(Au-TiO_2)纳米复合体,并以其作为SERS活性基底对吸附在其表面的探针分子(4-MBA)进行SERS研究。与纳米TiO_2上本征的SERS增强相比,适量的Au沉积导致复合基底对4-MBA分子具有更强的SERS增强效应,4-MBA的SERS信号增强来源于贵金属和半导体的共同作用;制备复合基底的光还原时间和氯金酸的浓度对复合基底的SERS增强效应均具有重要的影响。     

TiO_2/Ag@CDs的构筑及其SERS研究

碳点(CDs),尺寸在1~10nm,由于其独特的结构和光学性质,以及良好的生物相容性,在太阳能电池、有机污染物的降解和检测,光学染料、生物标记方面有着广泛的应用~([1])。TiO_2作为一种半导体材料,其粒子具有表面效应,量子尺寸效应,宏观量子隧道效应,催化等性质,可作为SERS基底。本文利用水热法成功制得粒径为2~6nm的发蓝光的CDs~([2]),然后在水浴下直接与TiO_2纤维和AgNO_3反应,形成在TiO_2表面包覆核壳结构的Ag@CDs纳米粒子复合物,TiO_2纤维长度和宽度不一,Ag@CDs平均尺寸在15nm左右,然后以TiO_2/Ag@CDs为SERS基底,PATP为探针分子,探究了其SERS性能,发现其检测的最低浓度可达到10~(-9) mol·L~(-1),具有良好的SERS增强能力。我们还分别研究了TiO_2/Ag@CDs的催化能力,用SERS监测了分子的变化过程,发现具有优良的催化性质,促进了CDs在SERS领域的应用。     

多功能Au/TiO_2/CoFe_2O_4材料用于原位SERS监测4-氯苯酚光催化过程

光催化降解性能不仅取决于光催化剂的组成与结构,而且还依赖于光催化剂界面上分子的转变机制。最近我们构建了一分层结构的Au/TiO_2/CoFe_2O_4复合材料,该材料既可作为高效光催化剂用于光降解4-氯苯酚(4-CP),又可作为SERS基底用于4-CP的SERS检测,同时兼具磁性利于回收循环使用。该多功能基底材料可以实现实时精确地原位SERS监测污染物分子在催化剂表面发生的光催化分子转化的详细信息,为准确识别反应中间体和深入了解光催化降解过程中的复杂反应机制提供了参考。     

Ag-Cu_2O/RGO纳米复合物的的制备及其SERS活性的研究

通过简单的化学还原法在室温条件下成功的合成了三元的Ag-Cu2O/RGO纳米复合物,这种复合物结合了Ag,Cu2O以及石墨烯三者的特性,表现出了很高的SERS活性。Cu2O/RGO具有一定表面增强能力,复合了Ag纳米粒子后,Ag-Cu2O/RGO纳米复合物对探针分子PATP的检测可以达到10-9 mol·L-1,一方面由于石墨烯比表面积大并具有大π键结构对分子起到了很好的富集作用,另一方面是由于Cu2O和Ag共同的SERS增强作用提高了SERS信号。因此该基底在SERS检测上有潜在的应用。     

Cu2O-Au复合材料表面甲基橙降解过程的原位SERS研究

SERS技术因其极高的表面灵敏度和选择性而成为表界面反应过程研究的重要工具之一,而光催化性能的调控建立在对其反应过程的分子水平的认识基础上,通过SERS基底与光催化材料的结合可实现催化反应过程的现场监测。本文制备了具备催化活性和SERS活性的双功能Cu₂O-Au复合材料,研究了其SERS增强和光催化降解甲基橙(MO)性能,并采用SERS技术现场研究了光催化降解MO的过程。研究表明,双功能Cu₂O-Au复合材料可将SERS效应和光催化性能有效复合,实现Cu₂O-Au界面处光催化降解过程的现场监测。表面Au纳米粒子的引入可使Cu₂O的SERS效应增强两个数量级,催化降解性能增加1倍;现场SERS监测揭示了光催化降解过程中MO分子的N=N最易断裂,C=C最难断裂,各化学键断裂容易程度由高到低依次为N=N> Ph₁-N=、=N-Ph₂ 以及Ph₁-N=、C-N> Ph-N。     

银/碳点复合纳米粒子的构筑及其SERS研究

碳点(CDs)作为一种新型的量子点,具有优良的发光性质,生物相容性和低毒性,以及易于化学修饰与功能集成性等优点。在光催化,光电器件,环境检测和生物成像领域有着广泛的应用[1]。碳点经常被直接使用,但最近其复合纳米粒子的研究受到越来越多关注,尤其与金属纳米粒子的复合不仅能保持两者各自本体的性质,而且具有协同作用带来的新功能。本文主要介绍了碳点作为还原剂直接还原硝酸银合成具有核壳结构的银/碳点纳米粒子,使碳点的荧光得以猝灭,得到碳点的D band和G band本征拉曼峰。然后以对巯基苯胺(PATP)为探针分子,研究了此核壳纳米粒子在溶液中的SERS性能,结果表明合成的Ag/CDs核壳纳米粒子具有稳定性好,检测限低等优点。另外Ag/CDs还具有良好的催化性能,可催化氧化TMB与催化还原PNTP,我们用SERS技术监测了整个催化过程,得到了被催化分子的变化信息,为其SERS定量与定性分析提供理论依据,扩展了碳点在SERS以及光催化领域的发展。     

Direct evidence for conversion of p‐aminothiophenol to p,p'‐dimercaptoazobenzene by in situ reduplicative surface‐enhanced Raman scattering measurements

There has been a surge of interest in the surface‐enhanced Raman scattering (SERS) of p‐aminothiophenol (PATP), since its SERS spectra are dependent on the measurement conditions. However, there is a dispute over the origin of the so‐called b₂ modes in SERS spectrum of PATP recently. Some researchers propose that these bands come from selective chemical enhancement, while others conclude that these bands are due to the a_g modes of p,p'‐dimercaptoazobenzene (DMAB) produced from PATP by surface photoreaction. To solve this problem, we have studied the SERS spectra of PATP on Au and Ag nanoparticles by in situ measurement under various conditions. The results proved that the b₂ modes are not due to PATP but due to the a_g modes of DMAB. The key of the method is to ensure the SERS spectra taken from the same point in reduplicative measurements. The result showed that the stable SERS spectrum of PATP was essentially from DMAB. The reversibility of the PATP SERS spectra in previous studies is due to the variety of the measurement points, which is in nature of different PATP conversions to DMAB under different conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and photocatalytic properties of silver nanoparticles loaded on CNTs/TiO2 composite

In this study, new nanoscale photocatalyst based on silver and CNTs/TiO₂ was successfully prepared by photoreduction method. The prepared Ag-CNTs/TiO₂ was characterized by TEM, XRD and XPS. The photocatalytic activity was also evaluated by photocatalytic degradation of Reactive Brilliant Red X-3B dye. The results indicated that the photocatalytic efficiency of CNTs/TiO₂ increased in the presence of Ag nanoparticles and the photocatalysis reaction followed a first order kinetics. The kinetic constant of Ag-CNTs/TiO₂ for dye degradation was nearly 1.2 times than that of CNTs/TiO₂, which indicated decorating Ag nanoparticles on CNTs/TiO₂ could enhance the photocatalytic ability.     

Seed‐mediated growth method for electroless deposition of AgNPs on glass substrates for use in SERS measurements

In this work, an electroless deposition method for silver nanoparticles (AgNPs) on glass substrates was developed for use in surface‐enhanced Raman scattering (SERS) measurements. To obtain evenly distributed AgNPs of suitable size on the glass substrates, a seeding procedure was utilized as a pretreatment before the electroless deposition of AgNPs. The AgNPs thus formed were affected by both the seeding and growing procedures. To optimize the procedures for preparation of SERS substrates, several factors, including reaction time, the concentration of silver ions, and the concentration of reducing agents (glucose) for seeding and growing procedures, were varied. The morphologies of the seeds and the resulting AgNPs on the glass substrates were characterized by field‐emission scanning electron microscopy (FE‐SEM) and correlated with the SERS signals from probing with para‐nitrothiophenol (pNTP). The results indicated that only the seeding time and the concentration of silver ions significantly influenced the distribution and sizes of the Ag seeds on the substrates. In the growing procedures, both the concentration of silver nitrate and the reducing agent affected the morphologies of the resulting AgNPs and, hence, the SERS signals. The substrates prepared using this newly developed method offer 2–5 times improvement of the SERS signals compared to substrates prepared without seed treatment. Also, the AgNPs prepared by this method can be easily controlled to designated sizes with even spatial and size distributions. Copyright © 2009 John Wiley & Sons, Ltd.     

SERS study on surface chain geometry of atactic poly (methyl methacrylate) film and nanosphere

The surface chain geometry of atactic poly (methyl methacrylate) (a‐PMMA) film and nanosphere (NS) was revealed by surface‐enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a‐PMMA film adopted a trans‐conformation on bonding to Ag surface ascribed to the short‐range chemical (CHEM) effect according to the SERS selection rules. However, for the well‐coated monolayer of a‐PMMA NSs, the α‐CH₃ in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a‐PMMA NSs and Ag metal was adopted the opposite orientation compared with a‐PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face‐centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above T_g of a‐PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well‐defined structure via a‐PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.     

A comparative study of surface‐enhanced Raman scattering from silver‐coated anodic aluminum oxide and porous silicon

Three types of Ag‐coated arrays from porous anodic aluminum oxide (AAO) were prepared and studied as substrates for surface‐enhanced Raman scattering (SERS). They were compared with Ag‐coated porous silicon (PSi) samples. AAO‐based substrates were prepared by the vapor deposition of silver directly onto the surface of porous AAO with different morphologies of the pores, whereas SERS‐active island films on the PSi were prepared by immersion plating. The resulting metallic nanostructures were characterized by UV‐vis absorption spectroscopy and scanning electron microscopy (SEM). Thermal evaporation leads to the formation of granular arrays of Ag nanoparticles on the surface of AAO. SERS activity of the substrates was tested using water‐soluble cationic Zn(II)‐tetrakis (4‐N‐methylpyridyl) porphyrin (ZnTMPyP4) as a probe molecule. The results indicate that all AAO‐based substrates studied here exhibit some degree of SERS activity. Noteworthy, for excitation at 532 nm, signals from AAO‐based substrates were comparable with those from the PSi‐based ones, whereas for 441.6 nm excitation they were about twice higher. The strongest SERS‐enhancement at 441.6 nm excitationwas provided by the AAO substrates with silver deposited on the monolith (originally nonporous) side of AAO. Preferential SERS‐enhancement of the bands ascribed to the vibrations of the N‐methylpyridinium group of ZnTMPyP4 when going to blue excitation was found. Copyright © 2010 John Wiley & Sons, Ltd.     

Improved performance of surface‐enhanced Raman scattering on silver substrates prepared in nitric acid solutions

In this work, we propose a new electrochemical method to prepare surface‐enhanced Raman scattering (SERS)‐active silver substrates in nitric acid solutions. Experimental results indicate that the SERS intensity of adsorbed Rhodamine 6G (R6G) can be significantly increased, as compared with that of R6G adsorbed on a SERS‐active Ag substrate prepared by an electrochemical method in a chloride‐containing solution, which was generally employed in the literature. Moreover, the SERS of R6G on the newly developed substrate (prepared in a nitric acid solution) still performs well at a high temperature of 250 °C. However, the enhancement capability of the SERS‐active substrate prepared in a chloride‐containing solution is seriously destroyed at temperatures higher than 150 °C. Further investigations indicate that the oxidation states of roughened Ag substrates prepared in nitric acid solutions under different experiment conditions have less influence on the corresponding SERS performances. Instead, different surface morphologies of roughened Ag substrates and different contents of nitrogen‐containing dopping ions on the roughened Ag substrates demonstrate significant effects on the corresponding SERS performances. Copyright © 2011 John Wiley & Sons, Ltd.     

Ag负载WO3/TiO2光催化剂的合成及其催化性能

以钛酸丁酯、无水乙醇、钨酸铵为原料,采用溶胶-凝胶法合成了WO3/TiO2复合光催化剂;采用光还原技术制备了Ag负载WO3/TiO2光催化剂,借助X射线粉末衍射(XRD)和UV-Vis光谱等技术对样品的组成和光吸收性能进行了表征,并以罗丹明B为模型污染物考察样品的光催化活性。XRD分析表明,所得粉体均为锐钛矿型纳米TiO2,且与WO3复合后,纳米TiO2特征衍射峰宽化,强度降低;UV-Vis光谱分析表明,载银使得催化剂在400—700nm的可见光区域对光响应,且在紫外光区吸收显著增强,对光具有更高的利用率;以罗丹明B为降解物的光催化实验表明,WO3复合对纳米TiO2光催化活性有显著的影响,而载Ag后其光催化活性进一步提高,将该光催化剂用于炼油厂废水的处理,效果较好。     

基于石墨烯基底的光催化特性

金属纳米结构中传导电子的集体振荡所产生的表面等离子体不仅可以使电磁场在时间和空间上重新分布,还可以使被激发的载流子重新分布.采用机械剥离法制备了石墨烯材料,借助拉曼光谱扫描技术(M apping)研究了石墨的层数在二维区域内的分布情况.研究了2-萘硫醇(2-N T)作为探针分子在石墨烯衬底上的SERS增强特性.结果表明...