铑电极上的表面增强拉曼光谱研究(英文)

本文简要介绍了将铑电极用于表面增强拉曼光谱 (SERS)研究的方法 .具有较强活性的铑电极可以通过对电极施加方波电流进行恒电流粗糙获得 .对模型分子吡啶进行的表面拉曼光谱研究表明 ,该电极具有很好的稳定性和可逆性 ,并且其表面增强因子可达 4 0 0 0 .在对铑电极上一氧化碳的氧化过程进行的拉曼光谱研究中同时检测到桥式和线型吸附的C O和Pt C振动的拉曼信号 .本研究表明铑电极可作为多用的SERS基底 ,拉曼光谱可作为界面研究的通用工具 .     

基于超微电极的原位电化学拉曼光谱

原位电化学拉曼光谱是一种重要的光谱电化学技术.基于超微电极的原位电化学拉曼光谱将拉曼光谱反映的结构信息与电极表面的电化学过程从实验上严格对应和关联,为深刻理解电化学反应机理提供依据.本文综述了采用超微电极作为工作电极的原位电化学拉曼光谱的研究方法和应用进展,总结了应用超微电极作为工作电极开展电化学拉曼光谱实验的方法和具有表面增强拉曼活性的超微电极制备方法,展示了如何利用在超微电极表面获得的拉曼光谱与界面电化学过程的严格关联研究单个锌颗粒电化学氧化过程、吡啶分子在Au电极表面的电化学吸附过程,以及如何利用该技术能以高的信噪比和灵敏度同时测量光电流与分子反应这一特性研究对巯基苯胺选择性光氧化反应.采用超微电极作为工作电极的原位电化学拉曼光谱技术极大拓展了拉曼光谱技术的研究范围,有望成为探索(光)电化学反应的有力工具.     

咪唑对锌缓蚀机理的表面增强拉曼光谱研究

利用电化学现场表面增强拉曼光谱技术(SERS)研究了咪唑在锌表面的成膜和缓蚀行为, 讨论了电位和pH值对咪唑分子和金属表面作用的影响. 锌电极上的表面拉曼光谱研究结果表明, 中性溶液中咪唑对锌的缓蚀作用明显, 它通过氮端垂直吸附在锌表面, 从而阻止锌的腐蚀, 其吸附取向不随电位的变化而改变; 在碱性溶液中咪唑和锌的作用较弱, 而且电位变化可以使其吸附取向发生改变, 在较正电位下咪唑以氮端垂直吸附, 在较负电位下以咪唑环倾斜吸附.     

寡聚脱氧核苷酸吸附状态随电位的变化

利用原位电化学及表面增强拉曼散射（SERS）光谱方法对寡聚脱氧核苷酸（26-mers ODN和13-mers ODN）在银电极表面上的吸附状态进行了研究. 实验表明, 单链寡聚脱氧核苷酸在银电极上有很好的SERS光谱,单链寡聚脱氧核苷酸在银表面上主要以碱基腺嘌呤（A）为吸附点,吸附状态随电位变化而变化, 链长较短的寡聚脱氧核苷酸在银电极表面的吸附态对电位变化较敏感.     

实用电极材料体系的共焦显微拉曼光谱研究(英文)

本文简要介绍了实验室内有关利用共焦显微拉曼光谱于某些实用电极材料 (表面 )性能研究的结果 .具体的研究实例包括 :尖晶石锂锰氧化物中Li+ 的嵌入 脱出过程 ,AB5 型金属氢化物电极表面氧化物的性能和钢筋电极表面钝化膜及其孔蚀过程 .     

电化学方法获得具有表面增强拉曼活性镍电极的研究

利用纯电化学手段获得了具有较强表面增强拉曼活性的镍电极, 改进了原有的镍电极表面预处理方法. 结果表明, 在0.5 mol/L的NaClO4溶液中, 结合电化学阶跃技术和循环伏安技术, 可以得到合适的粗糙镍电极; 同时, 还得到了探针分子吡啶在该粗糙镍电极表面随电极电位变化的表面增强拉曼光谱(SERS), 此时谱峰强度获得了极大的增强; 还研究了粗糙镍电极的扫描电子显微镜(SEM)图像, 并估算出其SERS增强因子约为104, 此结果比以前的镍电极表面粗糙方法所能达到的增强因子高一个数量级.     

具有纳米结构的铂电极表面的电化学制备及其性能

采用控电位方波氧化还原法和控电流方波氧化还原法分别成功地制备了控电位粗糙铂(CPRPt)和控电流粗糙铂(CCRPt)纳米级铂电极表面.通过考察两类电极表面对甲醇电催化氧化的性能,发现CPRPt和CCRPt纳米级铂电极表面催化氧化甲醇峰值电流密度分别是光滑铂电极的约1.35倍和2.50倍.采用现场拉曼光谱技术考察了两电极表面的表面增强拉曼(SERS)效应,发现两电极表面对吡啶吸附均有较高SERS活性,CPRPt电极表面还对有机小分子的解离吸附的拉曼光谱具有特殊的增强效应.本文初步探讨了两电极表面的SERS机理.     

苯在铑电极上吸附的表面增强拉曼散射光谱研究

利用成熟的电极处理方法成功地获得了苯在粗糙铑电极上电化学吸附的拉曼谱图.详细探讨了电极电位、电解质等因素对苯的电化学吸附的影响.结果表明,苯分子吸附到粗糙铑电极上后,表面拉曼谱图与纯苯本体谱图的差别很大,说明吸附后的苯分子在几何及电子结构上发生了巨大变化.苯分子可能以1,3-环己二烯的结构吸附于铑电极表面.     

单晶电极界面反应过程的电化学原位拉曼光谱研究

自20世纪70年代起,人们利用原位光谱技术（拉曼、红外等）对电化学界面进行了系统的研究,进而发展出原位谱学电化学的研究方向,由于其具有良好的表面灵敏度和能量分辨率,可以提供更多的表面反应信息,进而从微观上揭示反应机理. 伴随着纳米技术的兴起,表面增强拉曼光谱技术取得了快速的发展. 近来,壳层隔绝纳米粒子增强拉曼光谱（shell-isolated nanoparticle-enhanced Raman spectroscopy,SHINERS）技术更是得到人们的广泛关注. SHINERS的出现为研究单晶模型电极上的催化反应提供了一种非常好的原位光谱技术. 本文主要对原位电化学SHINERS技术在单晶电极界面研究的具体应用及其发展前景进行相关论述.     

免标记地检测二元磷脂膜中磷脂分布的表面增强拉曼成像方法

以银纳米粒子自组装层为增强基底,我们报道了一种用于检测二元磷脂膜中具有相似结构磷脂分布的表面增强拉曼成像方法,这种方法具有免标记及花费低廉的优点.对探针分子对巯基苯胺（p-aminothiophenol）,实验中所用的银纳米粒子自组装层表现出强的表面增强拉曼活性及良好的重现性.原子力显微镜表征结果证明了完整的磷脂膜在银纳米粒子自组装层上的形成.以这种银自组装层为基底,我们得到了磷脂膜中二肉豆蔻酰磷脂酰甘油（DMPG）和二肉豆蔻酰磷脂酰胆碱（DMPC）的表面增强拉曼光谱,并且利用DMPG的光谱特征峰,1482cm-1,区分这两种磷脂.而通过1482cm-1和1650cm-1的峰强比（R1482/1650）,可以同时得知在混合磷脂膜上某点这两种磷脂所占的比例：R1482/1650值的增加意味着DMPG的增加和DMPC的减少.磷脂膜的表面增强拉曼成像则是由R1482/1650值和对应的位置信息组合而得到,其成像结果表明了带电的磷脂DMPG在混合磷脂膜中的聚集.我们所报道的基于表面增强拉曼成像技术的方法提供了一种便利的、免标记的和花费低廉的途径来研究磷脂膜的结构,例如磷脂域和脂阀.     

Surface-enhanced vibrational spectroscopy of B vitamins: what is the effect of SERS-active metals used?

Surface-enhanced Raman scattering (SERS) spectroscopy and surface-enhanced infrared absorption (SEIRA) spectroscopy are analytical tools suitable for the detection of small amounts of various analytes adsorbed on metal surfaces. During recent years, these two spectroscopic methods have become increasingly important in the investigation of adsorption of biomolecules and pharmaceuticals on nanostructured metal surfaces. In this work, the adsorption of B-group vitamins pyridoxine, nicotinic acid, folic acid and riboflavin at electrochemically prepared gold and silver substrates was investigated using Fourier transform SERS spectroscopy at an excitation wavelength of 1,064 nm. Gold and silver substrates were prepared by cathodic reduction on massive platinum targets. In the case of gold substrates, oxidation–reduction cycles were applied to increase the enhancement factor of the gold surface. The SERS spectra of riboflavin, nicotinic acid, folic acid and pyridoxine adsorbed on silver substrates differ significantly from SERS spectra of these B-group vitamins adsorbed on gold substrates. The analysis of near-infrared-excited SERS spectra reveals that each of B-group vitamin investigated interacts with the gold surface via a different mechanism of adsorption to that with the silver surface. In the case of riboflavin adsorbed on silver substrate, the interpretation of surface-enhanced infrared absorption (SEIRA) spectra was also helpful in investigation of the adsorption mechanism.     

Surface-enhanced Raman scattering of pyridine using different metals: differences and explanation based on the selective formation of alpha-pyridyl on metal surfaces

A simple method has been developed to produce SERS-active metal surfaces. Six metal surfaces (cadmium, nickel, gold, iron, copper, and silver) have been prepared on an aluminum foil underlayment by chemical reduction and strong surface-enhanced Raman signals have been observed for pyridine species on these surfaces. This permits the direct comparison of pyridine spectra on different metal surfaces prepared by the same chemically clean method. The differences among the SER spectra of the aqueous pyridine species using different metals generally follow the trend of silver, cadmium, nickel, iron, gold, and copper, which can be explained by the selective formation of alpha-pyridyl species and the equilibria between end-on adsorbed pyridines and edge-on adsorbed alpha-pyridyl species on the different metal surfaces.     

Adsorption Behaviors of 4-Mercaptobenzoic Acid on Silver and Gold Films

The adsorption behaviors of 4-mercaptobenzoic acid on silver and gold nanoparticles were studied by surface-enhanced Raman scattering (SERS) and density functional theory. The silver and gold films by electrodeposition have the same excellent characteristics as SERS-active substrates. At the same, the SERS spectra indicate that 4-mercaptobenzoic acid molecules are adsorbed on the surfaces of gold nanoparticles through the S atom, and that the carboxyl group is far away from surface of gold nanoparticles, and that there is a certain angle between the plane of benzene ring and gold film. However, 4-mercaptobenzoic acid molecules are adsorbed on the surfaces of silver nanoparticles through the carboxyl group, and the S atom is far away from surface of silver nanoparticles, and there is also a certain angle between the plane of benzene ring and the surface of silver nanoparticles. Here it is demonstrated the calculated Raman frequencies are in good agreement with experimental values, and the calculated Raman frequencies are also helpful to infer the adsorption behaviors of 4-mercaptobenzoic acid molecules.     

Effects of the Roughening Procedures on Surface Enhanced Raman Scattering from Iron Electrodes

For about two decades, SERS has almost been restricted to the study of Ag, Au and Cu, which has impeded the wide application of Raman spectroscopy in surface science. Various efforts have been made in order to extend surface Raman spectroscopic studies to other metals, especially transition metals. In one of these approaches,particles or thin-layers of silver or gold are deposited on the surface of interest to enhance the Raman signal of species in the immediate vicinity.     

Surface-enhanced Raman scattering of some water insoluble drugs in silver hydrosols

An extraction method has been used to obtain surface-enhanced Raman scattering (SERS) spectra of water insoluble drugs such as aspirin, salicylic acid, acetaminophen, and vitamin A acid. This method is based on the strong affinity of the sample molecules to the silver particle surfaces. Results from the present study indicate that the method can be extended to identify and analyze many other water insoluble compounds by SERS. The high sensitivity of SERS and the linear calibration curve make it feasible in the trace quantitative analysis; the low limit of detection is comparable or better than those of calorimetric and spectrophotometric methods.     

Enhanced and normal Raman scattering from pyridine adsorbed on rough and smooth silver electrodes

A multiplex spectrograph has been used to record potential difference and modulation Raman spectra of pyridine adsorbed on silver electrodes in an electrochemical cell. Spectra have been obtained from rough silver surfaces which give SERS and from surfaces where SERS has been diminished by prolonged cathodic polarisation (DSERS). Raman scattering from pyridine at smooth silver surfaces in potassium perchlorate and fluoride solutions has been distinguished from solution scatter by a potential modulation technique. The results show that the enhanced scattering caused by silver atom or cluster sites is respresentative of the surface as a whole as similar Raman spectra are obtained on smooth surfaces at a count rate as low as ?1.4 photons s^?1 (incident laser power 500 mW).Correlation of simultaneous differential capacitance data and “snapshot” SER spectra indicate that pyridine molecules in aqueous chloride ion solutions adsorb on silver in a flat π-bonded configuration at potentials markedly positive to the point of zero charge and exhibit specific reorientation at ?0.3 V and ?0.45 V (vs. SCE) to become N-bonded, perpendicular to the surface. Results also show that the adsorption behaviour of pyridine in chloride and fluoride ion solutions is largely similar.     

Surface Enhanced Raman Scattering Sensing with Nanostructures Fabricated by Soft Nanolithography

The nanospike structures formed with femtosecond laser irradiations have been successfully replicated on the surface of a polyurethane (PU) polymer using a low cost soft nanolithography method. The surface enhanced Raman scattering (SERS) of rhodamine 6G (Rh6G) and dinitrotoluene (DNT) molecules have been measured with silver coated PU nanospike surfaces by a simple portable Raman spectrometer. Compared to a flat silver coated surface, where no Raman Scattering of the molecules can be detected by the simple portable Raman spectrometer, the Raman spectra are enhanced by more than 4 orders of magnitudes. This indicates that the high area/volume ratio and small size of the PU nanospikes can be used for SERS sensing.     

金与银电极表面甘氨酸分子吸附作用的SERS光谱研究

本文利用表面增强拉曼光谱(SERS)技术研究了甘氨酸在金与银基底表面的吸附作用特征。研究表明甘氨酸分子以COO-的不对称形式吸附于金电极表面,且NH2也是其可能的吸附位点;而在银电极表面,则主要是通过COO-的对称形式而吸附。在此基础上,进一步研究了电极电位与溶液酸碱性对吸附于粗糙化银电极表面甘氨酸分子吸附作用的影响。研究结果表明,甘氨酸分子中去质子化羧基的吸附作用受电位影响较小,而电位对-NH3+吸附作用的影响程度较大。另一方面,溶液pH值对银电极表面的甘氨酸分子吸附行为的影响也较为显著。随着溶液酸性减小羧基倾向于相对于电极表面平行吸附。这是由于随着溶液碱性增大氨基质子化程度的减小,有利于氨基在银电极表面吸附。这将改变分子的吸附构型使其更接近于电极表面。这些变化主要出现在pH值大于10的条件下。     

Raman spectral study of metal-cytosine complexes: a density functional theoretical (DFT) approach

The fluctuation of surface-enhanced Raman scattering (SERS) spectra has been an obstacle to the analysis of the adsorbate on the metal surface. In this paper, we aim at using the density functional theory (DFT) to study the fluctuant Raman spectra of the cytosine molecule which interacts with a coinage metal atom or cation via N1 and N3 sites. The results show that the adsorption site strongly influences the Raman spectral property of cytosine molecule, especially the relative intensity of some bands. In addition, the SERS spectra of cytosine which is adsorbed on the gold, silver, and copper electrodes are measured, and the possible orientation and adsorption site of the cytosine molecule adsorbed on metal electrodes surface are proposed with the help of DFT simulations.     

Surface Enhanced Raman Imaging of Adsorbate-Covered SERS Active Gold Nano-Particles

Surface enhanced Raman imaging (SERI), the combination of surface enhanced Raman scattering (SERS) and micro-Raman imaging, has recently been developed as a surface imaging technique. It offers the high sensitivity together with chemical information at high two-dimensional spatial resolution. For example, Yang et al. have reported the study of SERI distribution on a roughened silver electrode in two-dimension. Recently a particular interesting application of this technique in our lab was to image the gold nano-particles, which were deposited on glassy carbon (GC) surfaces.