离子液体中Fe电极界面结构的SERS光谱研究

采用高灵敏度的表面增强拉曼光谱(SERS)技术, 结合不同长度的探针分子, 通过电化学调控研究了Fe电极在离子液体中的表面增强因子、零电荷电位、界面吸附及界面双电层结构. 利用壳层隔绝纳米粒子增强拉曼光谱(SHINERS)技术提高表面吸附物种的拉曼信号, 降低高浓度本体的信号干扰, 研究了1-丁基-3-甲基咪唑四氟硼酸盐([BMIm]BF₄)离子液体本身在Au@SiO₂修饰的Fe电极表面的吸附行为. 结果表明,[BMIm]BF₄在Au@SiO₂修饰的Fe电极表面的吸附行为随电位变化而变化. 在-1.3 V以正区间, 咪唑阳离子以垂直吸附为主, 随电位负移逐渐倾斜甚至平躺吸附于电极表面; 当电位负至-2.3 V, 咪唑阳离子还原成卡宾. 再分别以不同分子长度的硫氰根(SCN^-)和4-氰基吡啶(4-CNPy)为探针分子, 发现SCN^-在[BMIm]BF₄中以N端吸附在纯Fe电极上, 三键频率随电位变化的速率, 即Stark系数为17 cm^-1/V; 4-CNPy以吡啶环上的N垂直吸附于Fe电极上, 频率保持不变, 即Stark系数接近零. 以上结果表明, 在离子液体中电极界面双电层与水体系的差别较大, 电位主要分布在电极紧密层中, 几乎无分散层存在. 此外, 还计算了[BMIm]BF₄中Fe电极的增强因子约为1.5×10².     

Au@SiO2膜/Ti电极吸附吡啶的表面增强拉曼光谱研究

基于壳层隔绝纳米粒子增强拉曼光谱技术,合成了Au@SiO₂纳米粒子,并对其进行了相关表征. 结果表明,包裹的二氧化硅层连续、致密,Au@SiO₂膜/Ti电极上可获得金属钛电极上吸附吡啶分子的高质量表面增强拉曼光谱（SERS）信号. 通过Pt、Ni电极的测试,证实该信号源于吸附在基底表面的吡啶分子. 此外,Au@SiO₂膜/Ti电极上吸附吡啶分子的现场SERS光谱研究表明,在-0.1 V ~ -0.6 V电位区间,吡啶分子平躺吸附,从-0.6 V起吸附的吡啶分子由平躺逐转变为垂直,而当电位为-1.2 V时,电极表面析氢,吡啶脱附.     

银电极上4-氨基安替比林原位表面增强拉曼光谱电化学

在银电极表面4-氨基安替比林(4-AAP)分子自组装,形成单分子膜层.应用表面增强拉曼散射(SERS)光谱原位考察不同电位下4-AAP在电极表面的吸附机理及其组装液pH值对组装分子与银作用方式的影响.依据密度泛函数(DFT)理论预测4-AAP分子振动模式及其SERS光谱归属.结果表明:在开路电位下,组装层中的4-AAP分子以N15和O3为位点,由苯环倾斜和比林环垂直的方式吸附在银表面;但随着外加电位负移,4-AAP分子的苯环趋于垂直吸附而比林环则逐渐以平行方式靠近银表面.在-0.8V电位下,4-AAP分子从银表面脱附.酸性溶液中组装,形成的4-AAP膜层以N15和O3为位点吸附于银表面,比林环倾斜而苯环直立;碱性条件下,分子的吸附位点不变,比林环呈平行取向,而苯环倾斜于银表面.     

电化学沉积法制备金（核）-铜（壳）纳米粒子阵列

以组装在有机分子自组装膜/金基底电极上的Au纳米粒子阵列为电化学沉积模板,制备了金(核)-铜 (壳)纳米粒子阵列.选用巯基十一胺（AUDT）和巯基癸烷（DT）混合自组装膜作为基底电极与Au纳米粒子的耦联层,可以在一定的电位下实现金属Cu在Au纳米粒子上的选择性沉积.将沉积电位控制在－0.03 V（vs SCE）时,沉积初期（t ≤ 15 s,沉积粒子粒径 ≤ 20 nm ）金(核)-铜 (壳)粒子具有良好的单分散性和近似球形,而且粒径实验值同计算值非常吻合.     

纳米金汞核-壳粒子的电化学制备及其光谱性质

在聚乙烯吡啶修饰导电玻璃电极表面进行了金纳米粒子的二维单层结构组装,通过电沉积方法在金粒子表面制备了纳米汞壳层.研究结果表明,汞壳层的形成导致了内部金粒子表面等离子体共振的谱峰红移和强度衰减.吸附于汞壳表面的结晶紫分子因可承受被金核增强的电磁场,而使其拉曼散射得到极大的增强.     

光催化还原制备Au/Ag核壳结构纳米粒子及其修饰电极的电催化性能

以Keggin结构硅钨杂多酸H4SiW12O40(SiW12)为光催化还原剂,通过光化学还原法制备Au/Ag核壳结构纳米粒子. 透射电子显微镜分析显示,所得纳米粒子粒径为30～40 nm,呈均匀分散的球形颗粒,该制备方法的特点是可以较好的避免单金属纳米粒子的形成. 将Au/Ag核壳纳米粒子修饰到具有PVP膜的玻碳电极表面,得到SiW12-(Au/Ag)-PVP多层膜修饰电极. 该修饰电极在0.5 mol/L H2SO4介质中具有良好的电化学响应,在0～-0.75 V电位范围内,出现了3对归属于SiW12的氧化还原峰,且电极性能稳定,灵敏度高. 对H2O2的电催化还原性能明显优于单金属Ag纳米粒子修饰电极,说明Au核的存在可以很好的改善Ag的电催化性能,Au和Ag之间存在相互协同催化作用.     

TiO2纳米晶电极上半菁衍生物分子设计中空间位阻效应的研究

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料 (E) N ( 4 磺酸根丙基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS) ,(E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS4)和 (E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]喹啉盐 (EQS4) ,研究了它们的光物理性质 ,并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池中 .研究发现 :对于吡啶类半菁染料而言 ,无论是以三个亚甲基或是以四个亚甲基来连接吸附基团RSO-3 和发色团时 ,单个的EPS和EPS4分子的光电响应行为一致 .但是由于以三个亚甲基来连接时 ,与EPS4相比 ,染料EPS的空间位阻相对较小 ,有利于其在多孔膜上的吸附 ,最终结果是染料EPS对TiO2 纳米晶电极的敏化作用好于EPS4.以喹啉环为受电子基团的染料EQS4与同样含有四个亚甲基的以吡啶环为受电子基团的EPS4相比 ,单个EQS4分子的光电响应行为虽然好于EPS4分子 ,但由于EQS4分子间的空间位阻较大 ,影响了它在多孔电极上的吸附 ,致使其敏化的太阳能电池的总光电转换效率有所下降     

Au@Pt纳米粒子单层膜对甲醇氧化的电催化性能及SERS研究

通过种子生长法合成Au@Pt核壳结构纳米粒子,采用两相成膜法制备单层粒子膜,并转移获得Au@Pt核壳纳米粒子单层膜电极,该电极表面纳米粒子分布均匀,具有较大的比表面,对甲醇的氧化具有较好的电催化活性.研究表明,利用内核Au的长程电磁场增强效应,该单层膜表现出均匀且优良的表面增强拉曼散射(SERS)活性,适合作为基底在分子水平上研究表面的吸附和反应.获得了Au@Pt核壳纳米粒子单层膜表面甲醇电催化氧化过程的SERS光谱,为深入分析表面反应机理提供了实验依据.     

Au@TiO2核壳纳米粒子光催化过程的表面增强拉曼光谱研究

利用聚电解质的静电吸附作用（层层组装）,在Au纳米粒子表面包裹上不同层数的二氧化钛前驱体TALH,通过退火形成Au@TiO2复合纳米粒子.以苯硫酚（TP）作为探针分子对退火前复合纳米粒子不同壳层厚度的SERS效应进行表征;可以发现：SERS信号强度的变化跟壳层厚度密切相关,当Au表面包裹至三层TALH时,信号几乎完全消失.此外,结合紫外照射,利用SERS对亚甲基蓝在TiO2壳层表面的光催化降解过程进行现场研究.结果表明：MB的降解主要经历了从多体及二聚体吸附逐渐向单体吸附方式转变,随后又经历了一个脱甲基的过程.因此,本工作发展了将一种紫外催化与现场SERS检测相结合的技术,该技术有望发展成为检测光催化过程,研究表面催化机理的一种强有力的工具     

电化学方法和表面增强拉曼光谱技术研究钴电极表面咪唑的吸附和缓蚀行为

利用电化学和表面增强拉曼光谱方法研究了咪唑和钴电极的相互作用. 分析并指认了不同电极电位下咪唑溶液中钴电极上的表面增强拉曼光谱(SERS), 发现随电极电位的变化, 在钴电极表面存在三种表面物种并且可以在一定程度上相互转化. 在较负电位(−1.2~−0.9 V)区间, 咪唑在钴电极表面以吸附物种为主, 随电位正移, 吸附取向由通过吡啶N垂直吸附逐渐向C2=N3双键倾斜; 在较正电位区间(−0.8~−0.7 V)内, 吸附咪唑的信号逐渐减弱乃至消失, 而钴和咪唑的络合物信号逐渐增强; 开路电位(−0.6 V)下出现很强的钴的氧化物谱峰. 同时, 文中比较了钴电极表面在空白溶液和加入咪唑后的溶液中的极化曲线, 发现咪唑对钴电极的缓蚀作用较为明显. 该研究结果表明, 联合表面增强拉曼光谱技术和电化学方法使得人们可以从分子水平上了解表面物种和电极表面间复杂的相互作用.     

锌电极上2-巯基吡啶自组装单层的原位表面增强拉曼光谱电化学观察

利用原位表面增强拉曼散射(SERS)技术, 观察了2-巯基吡啶在锌电极上单层吸附和脱附行为. SERS实验结果表明, 2-巯基吡啶分子主要通过巯基上的硫原子垂直吸附于锌表面. 原位SERS光谱电化学发现, 当外加电位达到－1.4 V vs. SCE时, 分子开始从表面脱附, 并伴随吸附构型变化, 在－1.6 V时发生完全脱附.     

苯胺在银和金电极上的表面增强拉曼光谱

聚苯胺作为性能较好的导电高聚物有很大的应用潜力,有关其聚合和导电机理的研究受到广泛重视。表面增强拉曼光谱(SERS)能现场(in situ)检测表面吸附分子、提     

Surface-enhanced Raman scattering (SERS) on silver electrodes as a technical tool in the study of the electrochemical reduction of cyanopyridines and in quantitative analysis

The SER spectra of 4-, 3- and 2-cyanopyridines adsorbed on a silver electrode are presented. The results show that cyanopyridines may adsorb in two different orientations, end-on (with the N atom of the Py ring bound to the surface) and flat, and that for potentials more negative than −1.1 V (SCE), the cyanopyridine radical anions can also be detected. The SERS intensity vs. potential curves show more than one potential of maximum SERS intensity which are assigned to the existence of more than one species on the electrode surface. The analytical potentially of SERS on electrodes has also been investigated. It is shown that the relative SERS intensity (ν_CN of the 4-CNPy (2120 cm⁻)/breathing mode of Py (1008 cm⁻¹)), at a fixed Py bulk concentration and at a fixed potential and exciting radiation, depends linearly on the 4-CNPy bulk concentration in the range 10⁻⁷-10⁻⁵M. The selectivity of the technique has also been investigated by studying the SER spectrum and the SERS intensity vs. potential curves for a mixture of 10⁻³M 4-CNPy, pyridine (Py) and 4-methylpyridine(4-MePy) in 0.1 M KCl aqueous solution.     

Adsorption and corrosion inhibition behavior of imidazole on cobalt electrodes studied by SERS and electrochemical methods

As one of the most widely used transition-metals, Co plays an important role in the study of metal mate-rials. The alloys of Co are often used as magnetic ma-terials because of their intense magnetism[1,2]. As an active metal and owing to high catalytic a…     

Electrochemical and surfaced-enhanced Raman spectroscopic investigation of CO and SCN- adsorbed on Au(core)-Pt(shell) nanoparticles supported on GC electrodes

Core-shell Au-Pt nanoparticles were synthesized by using a seed growth method and characterized by transmission electron microscopy, X-ray diffraction, and UV-vis spectroscopy. Au(core)-Pt(shell)/GC electrodes were prepared by drop-coating the nanoparticles on clean glassy carbon (GC) surfaces, and their electrochemical behavior in 0.5 M H2SO4 revealed that coating of the Au core by the Pt shell is complete. The electrooxidation of carbon monoxide and methanol on the Au(core)-Pt(shell)/GC was also examined, and the results are similar to those obtained on a bulk Pt electrode. High quality surface-enhanced Raman scattering (SERS) spectra of both adsorbed CO and thiocyanate were observed on the Au(core)-Pt(shell)/GC electrodes. The potential-dependent SERS features resemble those obtained on electrochemically roughened bulk Pt or Pt thin films deposited on roughened Au electrodes. For thiocyanate, the C-N stretching frequency increases with the applied potential, yielding two distinctly different dnu(CN)/dE. From -0.8 to -0.2 V, the dnu(CN)/dE is ca. 50 cm(-1)/V, whereas it is 90 cm(-1)/V above 0 V. The bandwidth along with the band intensity increases sharply above 0 V. At the low-frequency region, Pt-NCS stretching mode at 350 cm(-1) was observed at the potentials from -0.8 to 0 V, whereas the Pt-SCN mode at 280 cm(-1) was largely absent until around 0 V and became dominant at more positive potentials. These potential-dependent spectral transitions were attributed to the adsorption orientation switch from N-bound dominant at the negative potential region to S-bound at more positive potentials. The origin of the SERS activity of the particles is briefly discussed. The study demonstrates a new method of obtaining high quality SERS on Pt-group transition metals, with the possibility of tuning SERS activity by varying the core size and the shell thickness.     

Orientation of 6-mercaptopurine SAMs at the silver electrode as studied by Raman mapping and in situ SERS

Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) on a silver electrode in acid and alkaline media were investigated by a combination protocol of the SERS technique with Raman mapping, and it was found that the adsorption mode of 6MP SAMs changed with the pH value of the environment. Quantum calculations for the vibrational mode were performed by the BLYP/6-31G method. 6MP was adsorbed on the silver electrode with a tilted orientation via S, N1, and N7 atoms in acid medium, while the SAMs adopted head-on adsorption modes with the S atom and the N1 atom anchoring the silver surface in alkaline medium. However, 6MP SAMs turned to the same upright orientation on the electrode through the S and N7 atoms when either acid or basic solution was removed. Stability of 6MP SAMs was observed by in situ SERS spectroelectrochemical measurements. The results reveal that the desorption potentials of 6MP SAMs formed under acid and alkaline conditions from the Ag electrode were at ca. -1.3 V and -1.6 V vs SCE, respectively.     

Electrochemical evaluation of 4-(dimethylamino)pyridine adsorption on polycrystalline gold

Using differential capacity and chronocoulometry, we have studied the electrosorption of 4-(dimethylamino)pyridine (DMAP) on polycrystalline gold electrode surfaces. Our results indicate that the orientation of DMAP is highly dependent on the electrode potential and electrolyte pH. At pH values at or above the primary pKa, the adsorbed species is DMAP and orients vertically on the electrode surface via the lone pair of electrons on the pyridine ring's nitrogen atom. At very low pH values (<3) the adsorbed species is the protonated ion, DMAPH+, which can be desorbed from the electrode surface when the metal's surface charge density is made appreciably positive of the potential of zero charge. At intermediate electrolyte pH, either DMAP or DMAPH+ is adsorbed on the surface depending on the electrode's potential. At negative charge densities, DMAPH+ lies nearly flat on the gold electrode and the surface coverage is correspondingly low. When the electrode is positively charged, the adsorbate undergoes a phase transition to a vertical orientation and is simultaneously deprotonated to DMAP. Our results rationalize the stability of DMAP-ligated gold nanoparticles as a function of pH and demonstrate that the ligand's surface coverage is the principal factor in determining the stability of the colloidal system.     

Extraordinary enhancement of Raman scattering from pyridine on single crystal Au and Pt electrodes by shell-isolated Au nanoparticles

We used shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) to systematically study the adsorption of pyridine on low-index Au(hkl) and Pt(hkl) single crystal electrodes. Our gold-core silica-shell nanoparticles (Au@SiO(2) NPs) boost the intensity of Raman scattering from molecules adsorbed on atomically flat surfaces. The average enhancement factor reaches 10(6) for Au(110) and 10(5) for Pt(110), which is comparable to or even greater than that obtained for bare gold NPs (a widely adopted SERS substrate). 3D-FDTD simulations reveal that this large enhancement is due to the transfer of the "hotspots" from NP-NP gaps to NP-surface gaps. We also found that the SHINERS intensity strongly depends on the surface crystallographic orientation, with differences up to a factor of 30. Periodic DFT calculations and theoretical analysis of dielectric functions indicate that this facet-dependence is predominantly governed by the dielectric property of the surface. The results presented in this work may open up new approaches for the characterization of adsorbates and reaction pathways on a wide range of smooth surfaces.     

Hydration processes of electrolyte anions and cations on pt(111), Ir(111), Ru(001) and Au(111) surfaces: coadsorption of water molecules with electrolyte ions

Water adsorption on Pt( 111) and Ru(001) treated with oxygen, hydrogen chloride and sodium atom at 20 K has been studied by Fourier transform infrared spectroscopy, scanning tunneling microscopy and surface X-ray diffraction. Water molecules chemisorb predominantly on the sites of the electronegative additives, forming hydrogen bonds. Three types of hydration water molecules coordinate to an adsorbed Na atom through an oxygen lone pair. In contrast, water molecules adsorb on electrode surfaces in a simple way in solution. In 1 mM CuSO4 + 0.5 M H2SO4 solution on an Au(111) electrode surface, water molecules coadsorb not only with sulfuric acid anions through hydrogen bonding but also with copper, over wide potential ranges. In the first stage of underpotential deposition (UPD), each anion is accommodated by six copper hexagon (honeycomb) atoms on which water molecules dominate. At any UPD stage water molecules interact with both the copper atom and sulfuric acid anions on the Au(111) surface. Water molecules also coadsorb with CO molecules on the surface of 2 x 2-2CO-Ru(001). All of the hydration water molecules chemisorb weakly on the surfaces. There appears to be a correlation between the orientation of hydrogen bonding water molecules and the electrode potential.