非水体系中甲醇在粗糙铂电极上解离吸附的表面增强拉曼 光谱研究

利用共焦显微拉曼系统和表面增强拉曼散射(SERS)效应研究了非水体系中甲醇在粗糙铂电极上的解离吸附过程。结果表明：甲醇在粗糙铂电极上解离吸附后产生了毒性中间物CO,在较负的电位区间内,H与CO共吸附于电极表面并影响CO的吸附行为,随电位正移,ν~P~t~-~C的变化可以用电化学Stark效应进行解释,而ν~C~~O的变化则是由于电化学Stark效应和CO偶极耦合的共同作用所引起的。     

自组装DNA吸附取向的表面增强拉曼光谱法研究

对金基体上自组装寡聚核苷酸探针杂交前后进行电化学非现场及现场表面增强拉曼光谱(SERS)研究.非现场SERS研究表明,杂交形成的dsDNA在基体表面以A型和B型两种构象同时存在,杂交过程可能伴随DNA链在基体表面吸附取向的变化.根据现场SERS研究结果可知,ssDNA及dsDNA的大多数SERS谱带强度随电极电位正移而降低,尤其是归属于碱基A的两种面外振动模式,谱带变化更为明显.利用SERS表面选择定则判断出随着电极电位由负向正变化,ssDNA及dsDNA螺旋吸附取向由垂直吸附向平躺吸附于金基体表面变化.     

甲酸在Pt-Ru/GC电极上氧化的SERS研究

采用循环伏安(CV)法、计时电流法和电化学原位表面增强拉曼散射光谱(SERS)技术研究了甲酸在Pt-Ru/GC电极上的氧化行为, 发现甲酸在Pt-Ru/GC电极上与在粗糙Pt电极上一样, 也能自发解离出强吸附中间体CO和活性中间体—COO－. 从分子水平证实钌的加入有利于提高电极对甲酸的电催化氧化活性, 当镀液中Pt：Ru的摩尔比从10∶1变化到1∶1, CO的氧化峰电位从0.41 V负移至0.35 V, 约负移了60 mV. Pt-Ru/GC(1∶1)电极与粗糙Pt电极相比, CO在电极表面氧化完毕的电位亦负移了约200 mV. 该研究结果表明, 电化学原位表面增强拉曼散射光谱技术可望成为研究电催化反应机理的普适谱学工具.     

苯乙炔吸附在金电极上的现场表面增强拉曼光谱研究

采用电化学现场表面增强拉曼光谱研究了苯乙炔在金电极上的吸附行为及表面反应过程. 负电位下拉曼光谱的变化表明, 苯乙炔分子的炔端碳与金属电极成键, 分子垂直吸附于金电极表面. 在所研究的负电位区间内, 分子在电极表面的吸附取向并未随电位发生改变. 电化学现场光谱研究表明, 苯乙炔分子随电位负移, 碳碳叁键被加氢还原. 通过对比苯乙烯的现场表面增强拉曼光谱发现, 在－0.6 V至－1.2 V的电位区间内, 苯乙炔经过中间步骤生成苯乙烯, 最终被完全加氢为苯乙烷.     

银电极表面异亮氨酸单分子膜结构和表面性质的表面增强拉曼光谱研究

利用表面增强拉曼光谱(SERS)技术研究了在粗糙化银电极表面吸附的异亮氨酸自组装单层膜结构及其表面性质随溶液酸碱性和电极电位改变的特征.研究结果表明溶液pH值的变化并没有显著改变异亮氨酸分子在银电极表面以去质子化羧基吸附为主的特征.借助于高氯酸根离子这一SERS光谱探针,对异亮氨酸单分子膜的表面酸碱性质进行了表征和分析.而就电位改变对该单分子膜结构的影响而言,在所研究的电位范围内,单分子膜中的异亮氨酸分子是通过去质子化羧基与氨基两个位点而吸附的,且吸附作用随电位负移而呈现有规律的变化.     

2,2′-联吡啶与锌电极作用的表面增强拉曼光谱研究

利用表面增强拉曼光谱(SERS)对2,2′-联吡啶分子在锌电极表面的吸附进行了研究. 实验表明, 2,2′-联吡啶和锌电极有较强的相互作用, 2,2′-联吡啶和锌表面的氧物种存在竞争吸附, 起始电位较正时, 氧物种的吸附使2,2′-联吡啶吸附电位负移；起始电位较负时, 2,2′-联吡啶的吸附抑止氧物种的吸附, 使其吸附电位正移, 且相同电位下氧化种的吸附量大大减少. 同时当电极电位由正往负移时, 吸附在锌表面的2,2′-联吡啶会发生构型转化, 在－1.3 V下以顺式构型垂直吸附, 而当电位负移至－1.4 V时则以反式构型吸附；而电极电位由负往正移时, 在研究电位区间内2,2′-联吡啶都以反式构型吸附, 不存在构型的转化.     

银表面罗丹明6G的电化学表面增强拉曼光谱研究

罗丹明6G（Rhodamine 6G,R6G）是单分子表面增强拉曼光谱（SM-SERS）研究中最常用的探针分子之一,对R6G分子在表面吸附行为的研究有助于了解R6G分子和表面的相互作用. 本文应用电化学和电化学表面增强拉曼光谱技术,研究不同电位下R6G的银电极表面的吸附行为. 结果表明,随着电位负移罗丹明6G在银表面上从垂直吸附转为倾斜吸附,该变化和碱性条件下吸附于金纳米粒子上R6G的吸附构象一致. 这说明,在部分单分子实验中所发现的R6G反常光谱其来源是单个R6G分子在表面吸附取向变化. 本研究对后续详细分析SM-SERS研究中单分子SERS谱峰变化的机制有一定的参考价值.     

乙醇在粗糙铂电极上解离吸附与氧化的原位SERS研究

采用循环伏安法和原位表面增强拉曼光谱（SERS）研究了乙醇在粗糙铂电极上的吸附和氧化行为,获得了乙醇在粗糙铂电极上解离吸附的表面增强拉曼光谱.研究表明,在酸性介质中,乙醇能在粗糙铂电极上自发地解离出强吸附物种CO,在低波数区检测到桥式和线性吸附CO的铂碳键的伸缩振动信息;乙醇在粗糙铂电极上的氧化反应受扩散步骤控制;从分子水平初步证实乙醇的氧化是通过双途径机理进行的.     

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.     

时间分辨表面增强拉曼光谱(TRSERS)研究硫脲衍生物与ClO4^-的共吸附行为

运用时间分辨表面增强拉曼光谱(TRSERS)结合电位双阶跃的方法, 研究了硫脲衍生物甲基硫脲(MTU)和烯丙基硫脲(ATU)在银电极表面与ClO4^-离子的共吸附行为, SERS强度-时间曲线表明它们各自相应的SERS谱峰强度随电位阶跃的响应速率不同, 离电极表面较近的基团的特征谱峰强度的响应速率较快; MTU以S端且垂直吸附在电极表面,ATU也以S端和表面发生化学吸附, 但整个分子斜躺吸附在电极表面上。     

Surface-enhanced Raman scattering studies of 1,10-phenanthroline adsorption and its surface complexes on a gold electrode

This paper reports on the interface processes of 1,10-phenanthroline (phen) at a roughened Au electrode by surface-enhanced Raman scattering (SERS) for the first time. Both the adsorption and coordination of phen on the roughened gold electrode have been studied. In comparison to the normal Raman spectrum of phen monohydrate, the frequency and relative intensity change significantly in the SERS spectra. As evidenced by cyclic voltammetry, the electrochemical behavior of the Au electrode is strongly modified by the adsorbed phen. It was found that a new pair of redox peaks appeared in the cyclic voltammogram only when both phen and X (X = Cl-, Br-) were present. Information on coordination bonds of Au-N and Au-X as well as on adsorbed bonds of Au-N(ad) and Au-X(ad), was obtained by the SERS spectra. In situ SERS investigations together with electrochemical measurements convincingly prove the formation of surface complexes 1,10-phenAu2X6 or [1,10-phenAuX2]AuX4 during the electro-oxidation process of Au while phen and X coadsorbed on the surface.     

基于活性金电极上硫代水杨酸自组装单分子层的电化学表面增强拉曼光谱

采用原位电化学表面增强拉曼光谱(EC-SERS)研究了硫代水杨酸(TSA)吸附在活性Au电极表面的自组装单分子层(SAMs).TSA在活性Au表面的化学吸附及不同酸碱度下的TSA浸饰单层膜的SERS光谱,表明随pH值的增加,峰强呈现2个不同的下降阶段.通过EC-SERS考察不同电富集时间和电位的影响,显示在酸性介质和0.7 V及70 s富集时间下,可以获得最大EC-SERS信号,并随着电位负移,信号逐渐减弱,直至基本消失,表明TSA分子在Au表面排布状态会随外加条件的改变而发生变化.通过计算TSA在不同pH值下的分布分数以及探针分子在不同电位下的增强因子(EF),结合SERS和EC-SERS的变化走势对比,得出TSA在活性Au表面自组装形成单分子层/膜的机理,指出由于TSA不同的电化学吸附取向,以及高负电位下的还原/脱附作用,使得Au表面拉曼活性降低,造成EF显著减小,不可逆地失去了SERS的活性.     

Electrodeposition of dendritic gold/silver nanaoparticles on disposable screen‐printed carbon electrode and its application of 4‐mercaptopyridine in in situ electrochemical surface‐enhanced Raman scattering

Column electrodes pretreated through oxidation–reduction cycles were traditionally used in electrochemical surface‐enhanced Raman scattering (SERS). In this study, a disposable screen‐printed carbon electrode was introduced into in situ electrochemical SERS through the electrodeposition of dendritic gold/silver nanoparticles (Au/AgNPs) onto the surface of the carbon working electrode to induce the SERS enhancement effect on the electrode. Scanning electron microscopy images showed that dendritic Au/AgNPs nanostructures could be fabricated under appropriate electrodeposition conditions and could present a minimum SERS factor of 4.25 × 10⁵. Furthermore, the absorbed behavior of 4‐mercaptopyridine was investigated under different potentials. The adsorption configuration was inferred to transform from ‘vertical’ to ‘lying‐flat’. The proposed new electrode combined with a portable Raman spectrometer could be useful in the identifying products or intermediates during electrochemical synthesis or electrochemical catalysis in in situ electrochemical SERS. Copyright © 2016 John Wiley & Sons, Ltd.     

电极表面Ag(δ+)-NH3络合物的表面增强拉曼散射效应

本文采用氧化还原循环处理电极首次得到Ag/0.1 mol L~(-1)NH_3+0.1 mol L~(-1)NH_4Cl体系中吸附在银电极上氨分子的表面增强拉曼散射(SERS)效应。按氨分子在电极表面上的吸附量为每平方厘米8×10~(15)计算, 增加因子为1.2×10~5。谱峰强度及位置随电极电位改变。吸附氨分子的SERS谱与Ag(NH_3)_2~+的正常拉曼光谱类似。本文结果表明电极表面上存在Ag(δ+)络合物, 它可能是SERS效应的活性中心, 用这个概念可较好地解释本文实验结果。通过谱图分析给出了Ag(δ+)表面络合物的可能结构模式。     

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.     

SERS of C60/C70 on gold-coated filter paper or filter film influenced by the gold thickness

SERS of C(60)/C(70) adsorbed on gold nanoparticles coated on filter paper or filter film was studied. As a new SERS substrate, dried gold-coated filter paper or filter film has a high SERS activity, whose enhancement factor can be up to about 10(5), because it avoided the influence of solvents in C(60)/C(70) solution and water in gold hydrosols. The influence of the gold thickness coated on filter paper or filter film to SERS of C(60)/C(70) adsorbed on gold nanoparticles was mainly discussed. It is indicated that the SERS effect of C(60)/C(70) was very sensitive to the distribution and aggregated characteristics of gold nanoparticles, and the SERS intensity of each mode increased at its own proportion, but it integrally tended to saturation when the thickness of colloidal gold coatings increased.     

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.     

金纳米粒子组装体系中偶联单分子层膜结构的SERS光谱表征与分析

通过分子自组装方法制备4,4′-二硫联吡啶(PySSPy)单分子膜修饰的金电极. 利用所形成的对巯基吡啶自组装单分子膜(SAMs)作为偶联层进行金纳米粒子有序膜的组装. 对该纳米粒子组装体系进行Raman光谱测定, 得到了具有良好信噪比的对巯基吡啶单分子膜的表面增强拉曼散射(SERS)光谱. 在此基础上, 进一步采用电化学现场SERS光谱技术研究了该纳米粒子组装体系的SERS光谱随电位变化的规律. 在该体系稳定的电位范围内表征对巯基吡啶单分子膜的特征谱峰1011与1093 cm^-1、1575与1610 cm^-1以及1206与1215 cm^-1这三对谱峰其强度随着所施加电位的改变呈现出明显的规律性. 分析表明, 偶联单分子层中吡啶环芳香性随着所施加电位的改变而有规律地变化是SERS光谱特征改变的内在原因.     

双氰胺在金团簇上吸附的密度泛函理论和表面增强拉曼光谱研究

双氰胺是氰胺的二聚体,具有亚氨式和氨式两种互变异构体.将表面增强拉曼光谱(SERS)与密度泛函理论(DFT)结合,研究了互变异构的双氰胺分子在金表面的吸附行为.通过理论计算获得了亚氨式和氨式双氰胺分子的能量、分子轨道和光谱信息,以及双氰胺分子吸附在金簇表面的SERS响应.计算结果表明两种异构化的双氰胺分子都与Au₃簇形成较稳定的复合物,并且双氰胺分子中N₂原子优先吸附在金簇表面.拉曼实验结果与计算结果较为吻合,进一步说明具有互变异构的双氰胺分子在金基底中共存,并通过N₂原子垂直吸附到金表面,符合SERS电磁场增强机制.