Double layer structure and adsorption/desorption hysteresis of neat ionic liquid on Pt electrode surface — an in-situ IR-visible sum-frequency generation spectroscopic study

The electrochemical interface between a polycrystalline Pt electrode and the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) has been studied by in-situ IR-visible sum-frequency generation (SFG) spectroscopy. Potential dependent adsorption/desorption processes of OTf anions has been monitored within the electrochemical window. SFG results indicate that the ions form a double layer structure at the interface. Significant adsorption/desorption hysteresis has been observed for the anions on the Pt surface.     

Structure of water at ionic liquid/Ag interface probed by surface enhanced Raman spectroscopy

The potential-dependent adsorption behavior of water and ionic liquid was probed by surface-enhanced Raman spectroscopy (SERS) at the Ag electrode surface in the ionic liquids containing water with different concentrations.The configuration of water at the ionic liquid/electrode interface and the relationship between the potential of zero charge (pzc) and the molar fraction of water were deduced through the changes in the vibrational frequency of OH stretching mode.A small Stark effect value was determined ...     

含水离子液体/金属界面结构的SERS研究

利用表面增强拉曼光谱(SERS)研究了不同含水量下离子液体及水分子在银电极上随电位变化吸附方式的改变,通过水的O-H伸缩振动谱峰频率变化特征,详细探究了水在离子液体/电极界面上的存在形式及作用方式以及体系零电荷电位与水含量的关系.水含量较低时O-H伸缩振动的Stark系数值较低,随水含量的增加O-H伸缩振动的谱峰位置逐渐向高波数方向移动,同时O-H伸缩振动的Stark系数也逐渐增大,1molL-1[BMIM]Br水溶液中达到76cm-1V-1,且体系的零电荷电位正移,这些差异与水在离子液体中所形成氢键的程度及水分子的存在形式密切相关,在水的含量较低时水与离子液体阳离子通过氢键作用而存在于界面层中,当水的含量增加时,水分子间氢键的作用增强,水与电极表面直接作用的可能性增大.     

Sum frequency generation study of the room-temperature ionic liquids/quartz interface

The purpose of this investigation is to study the ionic liquid/quartz interface with sum frequency generation vibrational spectroscopy (SFG). SFG spectroscopy was chosen for this study because of its unique ability to yield vibrational spectra of molecules at an interface. Different polarization combinations are used, which probe different susceptibilities, giving SFG the ability to determine molecular orientation at the interface. The ionic liquids used were 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF(4)], and 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)]. To determine the influence of the molecular structure and charge on orientation at the interface, neutral, 1-methylimidazole, and 1-butylimidazole were also studied. Raman spectra and depolarization ratios were obtained for neat samples of 1-methylimidazole, 1-butylimidazole, and 1-butyl-3-methylimidazolium tetrafluoroborate recorded from 2700 to 3300 cm(-1). SFG spectra of the 1-methylimidazole/quartz interface showed both methyl and aromatic C-H vibrations. Orientation calculations determined that the ring of the molecule is tilted 45-68 degrees from normal, with the methyl group oriented 32-35 degrees from normal. The SFG spectra of 1-butylimidazole contain several resonances from the alkyl chain with only one weak resonance from the aromatic ring. Orientation calculations suggest that the ring is lying in the plane of the surface with the methyl group pointing 43-47 degrees from normal. The orientation of the [BMIM][PF(6)] ionic liquid was sensitive to trace amounts of water and had to be evacuated to <3 x 10(-5) Torr for the water to be removed. SFG spectra of both ionic liquids were similar, displaying resonances from the alkyl chain as well as the aromatic ring. Orientation analysis suggests the aromatic ring was tilted 45-90 degrees from normal for [BMIM][BF(4)], while the ring for [BMIM][PF(6)] was tilted 38-58 degrees from normal. This suggests the orientation of the molecule is influenced by the size of the anion.     

碱性体系中金电极表面硫氰根离子的宽带和频光谱研究

本文使用宽带和频光谱研究不同电位下碱性溶液中多晶金电极表面硫氰根离子（SCN^-）的吸附行为. 在-1.1 V ~ 0.2 V（vs. SCE）,C-N伸缩振动的Stark斜率的变化表明,随着电位正移,SCN^-在金电极表面从N端吸附变为S端吸附. 在较正电位下,C-N伸缩振动具有Fano线型. 这是因为金的费米能级随电位的正移而降低,和频过程中金的电子跃迁方式从带内跃迁（sp→sp）变为带间跃迁（d→sp）,造成金基底与表面吸附SCN^-和频信号的相对相位改变. 实验表明,通过研究和频光谱线型随电位的变化可以获取电极表面电子能级相对位置的信息.     

In situ electrochemical SFG/DFG study of CN⁻ and nitrile adsorption at au from 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ionic liquid([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]diazenyl} benzonitrile (CTDB) and K[Au(CN)₂

In this paper we report an in situ electrochemical Sum-/Difference Frequency Generation (SFG/DFG) spectroscopy investigation of the adsorption of nitrile and CN? from the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]-diazenyl}benzonitrile (CTDB) at Au electrodes in the absence and in the presence of the Au-electrodeposition process from K[Au(CN)?]. The adsorption of nitrile and its coadsorption with CN? resulting either from the cathodic decomposition of the dye or from ligand release from the Au(I) cyanocomplex yield potential-dependent single or double SFG bands in the range 2,125-2,140 cm?1, exhibiting Stark tuning values of ca. 3 and 1 cm?1 V?1 in the absence and presence of electrodeposition, respectively. The low Stark tuning found during electrodeposition correlates with the cathodic inhibiting effect of CTDB, giving rise to its levelling properties. The essential insensitivity of the other DFG parameters to the electrodeposition process is due to the growth of smooth Au.     

Anion configuration at the air/liquid interface of ionic liquid [bmim]OTf studied by sum-frequency generation spectroscopy

The air/liquid interface of a room temperature ionic liquid, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim]OTf), is investigated using infrared-visible sum frequency generation (SFG) spectroscopy. The SFG spectra clearly show low-frequency modes [CF 3-symmetric stretching (ss) mode and SO 3-symmetric stretching (ss) mode] of the OTf anion, demonstrating the existence of anions polar oriented at the interface. The amplitude of the CF 3-ss peak of the OTf anion has the opposite sign with respect to that of the SO 3-ss peak, indicating that OTf anions at the surface have polar ordering where the nonpolar CF 3 group points away from the bulk into the air, whereas the SO 3 group points toward the bulk liquid. The line width of the SFG peak from the submerged SO 3 group is appreciably narrower than that from IR absorption, suggesting the environment of the surface OTf anions is much more homogeneous than that of the bulk. The vibrational calculations also suggest that the anions and the cations form a more specific aggregated configuration at the surface as compared to the bulk.     

Adsorption of 1- and 2-butylimidazoles at the copper/air and steel/air interfaces studied by sum frequency generation vibrational spectroscopy

The structure of thin films of 1- and 2-butylimidazoles adsorbed on copper and steel surfaces under air was examined using sum frequency generation (SFG) vibrational spectroscopy in the ppp and ssp polarizations. Additionally, the SFG spectra of both isomers were recorded at 55 °C at the liquid imidazole/air interface for reference. Complementary bulk infrared, reflection-absorption infrared spectroscopy (RAIRS), and Raman spectra of both imidazoles were recorded for assignment purposes. The SFG spectra in the C-H stretching region at the liquid/air interface are dominated by resonances from the methyl end group of the butyl side chain of the imidazoles, indicating that they are aligned parallel or closely parallel to the surface normal. These are also the most prominent features in the SFG spectra on copper and steel. In addition, both the ppp and ssp spectra on copper show resonances from the C-H stretching modes of the imidazole ring for both isomers. The ring C-H resonances are completely absent from the spectra on steel and at the liquid/air interface. The relative intensities of the SFG spectra can be interpreted as showing that, on copper, under air, both butylimidazoles are adsorbed with their butyl side chains perpendicular to the interface and with the ring significantly inclined away from the surface plane and toward the surface normal. The SFG spectra of both imidazoles on steel indicate an orientation where the imidazole rings are parallel or nearly parallel to the surface. The weak C-H resonances from the ring at the liquid/air interface suggest that the tilt angle of the ring from the surface normal at this interface is significantly greater than it is on copper.     

Surface orientation of 1-methyl-, 1-ethyl-, and 1-butyl-3-methylimidazolium methyl sulfate as probed by sum-frequency generation vibrational spectroscopy

The orientation of the ions at the surface of ionic liquids has been determined by the surface-sensitive technique sum-frequency generation vibrational spectroscopy. The results indicate that both ions are present at the first layer of the gas-liquid interface. Furthermore, the alkyl chains are found to be extended toward the gas phase and away from the liquid phase. The proposed models for the preferred orientation of the ions are in good agreement in comparison with the results obtained from the recent MD simulation studies. The salts considered here are 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfate, and 1-butyl-3-methylimidazolium methylsulfate.     

Surface characterization of 1-butyl-3-methylimidazolium Br-, I-, PF6-, BF4-, (CF3SO2)2N-, SCN-, CH3SO3-, CH3SO4-, and (CN)2N- ionic liquids by sum frequency generation

Sum frequency generation spectroscopy, SFG, was used for the surface characterization at the gas-liquid interface of the 1-butyl-3-methylimidazolium cation combined with the following anions: Br-, I-, PF6-, BF4-, (CF3SO2)2N- (imide), SCN-, CH3SO3- (MeSO3), CH3SO4- (MS), and (CN)2N- (DCN). The SFG spectra obtained for the different ionic liquids were similar independent of the anion selected; therefore, a comprehensive analysis for the surface characterization of the ionic liquids' cation was focused only on the PF6- and Br- anion combinations. For an accurate identification of the vibrational modes observed, FT-IR and Raman spectroscopy in combination with isotopic labeling with deuterium and polarized Raman spectroscopy was used. The cation orientation was determined by analysis of polarization-dependent SFG spectra. For a compound dried in a vacuum to < or = 2 x 10(-5) Torr, the cation appears to be oriented with the ring laying flat along the surface plane and the butyl chain projecting into the gas phase independent of the anion identity.     

离子液体中硫氰根在铂电极上吸附行为的SERS研究

利用表面增强拉曼光谱(SERS)研究了室温离子液体1-丁基-3-甲基咪唑氟硼酸盐([BMIM]BF4)中SCN-在Pt电极表面的吸附行为. 研究结果表明, 离子液体中SCN-在较宽的电位范围内吸附在Pt电极上, 且SCN-的吸附方式随着电位区间的变化而变化, 在不同的电位区间内检测到了不同的Stark位移: -0.9~0.4 V约为34 cm-1/V, 对应于S端吸附; -1.6~-1.2 V约为40 cm-1/V, 该区间以N端吸附为主, 中间电位区间为吸附方式的转变区, 且Pt电极在离子液体[BMIM]BF4中的零电荷电位约为-1.1 V(vs. Pt ).     

Local structure at the air/liquid interface of room-temperature ionic liquids probed by infrared-visible sum frequency generation vibrational spectroscopy: 1-alkyl-3-methylimidazolium tetrafluoroborates

The air/liquid interface of 1-alkyl-3-methylimidazolium tetrafluoroborates with the general formula [C(n)mim]BF(4) (n = 4-11) was studied using infrared-visible sum frequency generation (SFG) vibrational spectroscopy. The probability of the gauche defect per CH2-CH2 bond in the alkyl chain decreases as the number of carbon atoms in the alkyl chain increases. This observation suggests that the interaction between the alkyl chains is enhanced as the alkyl chain length becomes longer. The frequencies of the C-H stretching vibrational modes observed in the SFG spectra are higher than those of the corresponding peak positions observed in the infrared spectra of the bulk liquids. This shift is consistent with a structure in which the alkyl chain protrudes from the bulk liquid into the air. A local structure, which originates from the intermolecular interaction between the ionic liquid molecules, is proposed to explain these observations.     

Alkanethiol monolayers at reduced and oxidized zinc surfaces with corrosion protection: a sum frequency generation and electrochemistry investigation

In this work, octadecanethiol (ODT) was demonstrated to form ordered monolayers at either electrochemically reduced or oxidized Zn surfaces, by means of sum frequency generation (SFG) spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The SFG spectra of ODT-modified Zn electrodes featured three methyl group resonances in the C-H vibrational region (2800-3100 cm(-1)). A significant decrease in interfacial capacitance and an increase in charge-transfer resistance were observed in EIS measurement after ODT modification. The alkane chain tilt angle of ODT within a monolayer at the Zn surface was estimated as 0 degrees with respect to the surface normal by interfacial capacitance measurement via EIS. CV and SFG investigation revealed that ODT monolayers undergo reductive desorption from the Zn electrode in 0.5 M NaOH at -1.66 V (vs SCE) and in 0.5 M NaClO4 at -1.62 V. The integrated charge consumed to the desorption of ODT is determined as 87 mC/cm2 from the reductive peak on CV curve, resulting in a coverage of 9.0 x 10(-10) mol/cm2 (5.4 x 10(14) molecules/cm2) if assuming the reduction follows a one-electron process. ODT monolayers show corrosion protection to underlying zinc at the early immersion stage in base, salt, and acid media. However, the protection efficiency was reduced with immersion time due to the presence of defects within the monolayers.     

Infrared plus vacuum ultraviolet spectroscopy of neutral and ionic ethanol monomers and clusters

A high sensitivity spectroscopy is employed to detect vibrational antiitions of ethanol neutrals and ions in a supersonic expansion. The infrared (IR) features located at 3682 and 3667 cm(-1) can be assigned to the OH stretch for the two neutral C(2)H(5)OH conformers, anti and gauche, respectively. Their overtone energies located at 7179 (anti) and 7141 (gauche) cm(-1) are also identified. The OH fundamental stretch for ethanol ions is redshifted around 210 cm(-1), while the CH stretch modes are unchanged for neutral and ionic C(2)H(5)OH at around 2900-3000 cm(-1). The charge on the ethanol ion is apparently localized on the oxygen atom. IR induced photodissociation spectroscopy is applied to the study of neutral and protonated ethanol clusters. Neutral and protonated ethanol cluster vibrations are observed. The CH modes are not perturbed by the clustering process. Neutral clusters display only hydrogen bonded OH features, while the protonated ionic clusters display both hydrogen bonded and non-hydrogen-bonded features. These spectroscopic results are analyzed to obtain qualitative structural information on neutral and ionic ethanol clusters.     

和频振动光谱研究多晶金电极/溶液界面乙腈分子取向的flip-flop行为

用和频振动光谱研究乙腈/金电极界面,观测到乙腈的甲基振动峰强度随施加的电极电势而变化.当电极电势越过零电荷电势（pzc）时,甲基振动峰符号发生反转,这意味着基团取向发生反转（flip-flop）.由此推断出乙腈分子在金电极界面的吸附构型.即在零电荷电势下,电极界面吸附的乙腈分子构型为甲基靠近电极表面而腈基远离电极表面;而高于零电荷电势则电极界面吸附的乙腈分子构型发生反转,变为腈基靠近电极表面而甲基远离电极表面的构型.     

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), ζ-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Probing alpha-helical and beta-sheet structures of peptides at solid/liquid interfaces with SFG

We demonstrated that sum frequency generation (SFG) vibrational spectroscopy can distinguish different secondary structures of proteins or peptides adsorbed at solid/liquid interfaces. The SFG spectrum for tachyplesin I at the polystyrene (PS)/solution interface has a fingerprint peak corresponding to the B1/B3 mode of the antiparallel beta-sheet. This peak disappeared upon the addition of dithiothreitol, which can disrupt the beta-sheet structure. The SFG spectrum indicative of the MSI594 alpha-helical structure was observed at the PS/MSI594 solution interface. This research validates SFG as a powerful technique for revealing detailed secondary structures of interfacial proteins and peptides.     

Demonstrating the feasibility of monitoring the molecular-level structures of moving polymer/silane interfaces during silane diffusion using SFG

In this paper, the feasibility of monitoring molecular structures at a moving polymer/liquid interface by sum frequency generation (SFG) vibrational spectroscopy has been demonstrated. N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (AATM, NH2(CH2)2NH(CH2)3Si(OCH3)3) has been brought into contact with a deuterated poly(methyl methacrylate) (d-PMMA) film, and the interfacial silane structure has been monitored using SFG. Upon initial contact, the SFG spectra can be detected, but as time progresses, the spectral intensity changes and finally disappears. Additional experiments indicate that these silane molecules can diffuse into the polymer film and the detected SFG signals are actually from the moving polymer/silane interface. Our results show that the molecular order of the polymer/silane interface exists during the entire diffusion process and is lost when the silane molecules traverse through the thickness of the d-PMMA film. The loss of the SFG signal is due to the formation of a new disordered substrate/silane interface, which contributes no detectable SFG signal. The kinetics of the diffusion of the silane into the polymer have been deduced from the time-dependent SFG signals detected from the AATM molecules as they diffuse through polymer films of different thickness.     

Electrode screening by ionic liquids

In this work we are concerned with the short-range screening provided by the ionic liquid dimethylimidazolium chloride near a charged wall. We study the free energy profiles (or potentials of mean force) for charged and neutral solutes as a function of distance from a charged wall. Four different wall charge densities are used in addition to a wall with zero charge. The highest magnitude of the charge densities is ±1 e nm(-2) which is close to the maximum limit of charge densities accessible in experiments, while the intermediate charges ±0.5 e nm(-2) are in the range of densities typically used in most of the experimental studies. Positively and negatively charged solutes of approximately the size of a BF ion and a Cl(-) ion are used as probes. We find that the ionic liquid provides excellent electrostatic screening at a distance of 1-2 nm. The free energy profiles show minima which are due to layering in the ionic liquid near the electrodes. This indicates that the solute ions tend to displace ionic liquid ions in the layers when approaching the electrode. The important role of non-electrostatic forces is demonstrated by the oscillations in the free energy profiles of uncharged solutes as a function of distance from the wall.