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1.
应用和频振动光谱研究乙腈/金电极界面吸附,观测到乙腈的甲基振动峰强度随电极电势而变化.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,这意味着该基团取向发生反转(flip-flop).由此而推断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...  相似文献   

2.
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.  相似文献   

3.
含水离子液体/金属界面结构的SERS研究   总被引:1,自引:1,他引:0  
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.  相似文献   

4.
建立了选择性电极中离子传递的模型,活化后的离子选择性电极,在电极表面形成活化层,阳离子和等量的阴离子分布在电极活化层的两侧,离子由溶液与活化的界面经活化层传递到固定组成膜与活化界面,在一定的条件下,电极膜电势随时间的变化与溶液和活化层的界面离子浓度随时间的变化成正比,在控制电势随时间的变化率基本恒定的情况下,方法被用于手工测量氟离子选择性电极电势,电极斜率,溶液离子浓度直接由Gran方程求解。  相似文献   

5.
建立了选择性电极中离子传递的模型。活化后的离子选择性电极 ,在电极表面形成活化层 ,阳离子和等量的阴离子分布在电极活化层的两侧 ,离子由溶液与活化层的界面经活化层传递到固定组成膜与活化层界面。在一定的条件下 ,电极膜电势随时间的变化与溶液和活化层的界面离子浓度随时间的变化成正比。在控制电势随时间的变化率基本恒定的情况下 ,方法被用于手工测量氟离子选择性电极电势 ,电极斜率。溶液离子浓度直接由 Gran方程求解。  相似文献   

6.
本文针对BMIPF6和OMIPF6两种离子液体,在电极表面远离零电荷电位且以负电荷表面电位下,运用AFM力曲线详细地研究了其与Au(111)单晶电极界面所形成的层状结构与温度的关联.在15~40oC的温度范围内,温度越低其离子液体层状结构越稳定.温度对OMIPF6离子液体层状结构的稳定性和数目的影响较BMIPF6缓和:温度变化5oC,OMIPF6靠近表面第一层层状结构的力值变化仅为1~2 nN,而BMIPF6第一层层状结构的力值变化为3~5 nN;较低温下,BMIPF6中层状结构的数目有所增加,而OMIPF6的层状数目始终保持两层,且随温度的变化并不敏感.这可归因于两种离子液体的阳离子尺寸以及与电极表面的作用方式和强度不同;同时,OMIPF6较粘稠,其热运动受温度的影响不甚敏感.  相似文献   

7.
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 ).  相似文献   

8.
在1-丁基3-甲基咪唑三氟甲基磺酸盐([Bnlim][CF_3SO_3])/碳酸丙烯酯(PC)溶液中,采用循环伏安曲线、交流阻抗谱及阻抗模拟方法,研究了CO_2在Au上发生电还原反应的速率控制步骤与离子液体的催化作用.结果表明,在CO_2电还原反应过程中,吸附态CO_2经单电子还原生成CO_2~-自由基是速率控制步骤.由于离子液体的催化作用,CO_2在[Bmim][CF_3SO_3]/PC溶液中电还原的过电位比在四丁基三氟甲基磺酸铵([Bu_4N][CF_3SO_3])/PC溶液中降低了239 mV.交流阻抗测试结果表明,离子液体中的阳离子[Bmim]~+吸附在Au电极表面,形成离子液体吸附层,吸附态的CO_2分子经单电子还原后生成CO_2~·-)自由基,与周围离子液体发生相互作用,形成中间体[Bmim-CO_2]_(ad),降低了CO_2~(·-)的能量状态,使得CO_2电还原反应的过电位大幅度降低.  相似文献   

9.
CH_2Cl_2对离子液体BmimPF_6中二茂铁电化学行为的影响   总被引:1,自引:0,他引:1  
应用循环伏安和交流阻抗法研究有机溶剂二氯甲烷对二茂铁在离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BmimPF6)中电化学行为的影响.实验表明, 二氯甲烷可促进离子液体的离子解离,减小离子液体粘度,增加离子液体电导率,加速二茂铁在离子液体中的扩散,增大氧化还原峰电流.由于电极界面双电层结构的变化,导致双电层电容增大,电极反应电阻减小,从而加速了界面电子传递反应.  相似文献   

10.
采用示差脉冲伏安法研究了自组装单层保护金纳米团簇(C8AuMPC)在常温下二氯甲烷溶液中的量子化电容充电效应. 研究结果表明, 该团簇在-0.8~0.8 V 电位范围内有4 对明显的量子化电容充电峰. 同时采用电化学阻抗谱对C8AuMPC修饰金电极体系的界面结构进行了表征, 研究结果表明, MPC自组装层存在两个界面, 即金电极-MPC层界面和MPC层-溶液界面; 这两个界面的界面电容在MPC的零电荷电位(ca.-0.2 V)附近均基本保持不变, 随着电位正移或负移到一定程度, 界面电容发生变化. 进一步利用双隧道结金属岛库仑阻塞效应理论讨论了已有报道中对MPC量子化电容充电的理论分析结果, 并证明电化学阻抗谱也是研究MPC量子化电容充电效应的有效方法. 另外, 用示差脉冲伏安法及循环伏安法研究了电活性物种二茂铁对C8AuMPC量子化电容充电的影响, 发现溶液中的电活性物种对MPC层-溶液界面的电子传递的贡献可以忽略, 表明该界面的电子传递主要发生在纳米粒子之间.  相似文献   

11.
The growth of gold nanoparticles (NPs) synthesized by sputter deposition on an ionic liquid surface is studied in situ in the bulk phase of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide [C(1)C(4)Im][N(CN)(2)], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [C(1)C(4)Im][Tf(2)N], 1-butyl-3-methylimidazolium tetrafluoroborate [C(1)C(4)Im][BF(4)], 1-butyl-3-methylimidazolium hexafluorophosphate [C(1)C(4)Im][PF(6)] and 1-butyl-3-methylimidazolium triflate [C(1)C(4)Im][TfO]. It is found that primary nanoparticles with a diameter smaller than 2.5 nm are present in the sample immediately after sputtering. Growth of these primary particles proceeds after the end of the sputtering process and stops when the nanoparticles reach a certain size. Depending on the viscosity of the ionic liquid this growth process can proceed several hours to several days. The growth speed is fastest for the least viscous ionic liquid and follows the trend [C(1)C(4)Im][N(CN)(2)] > [C(1)C(4)Im][Tf(2)N] > [C(1)C(4)Im][TfO] > [C(1)C(4)Im][BF(4)] > [C(1)C(4)Im][PF(6)]. It is also found that a higher concentration of sputtered gold results in faster growth of the gold nanoparticles. A discussion on the growth mechanism of sputtered gold NPs is included.  相似文献   

12.
The surface tensions were measured at atmospheric pressure, with use of a ring tensiometer, of a series of alcoholic solutions of closely related ionic liquids: 1-methyl-3-methylimidazolium methylsulfate, [MMIM][CH3SO4] in alcohol (methanol, or ethanol, or 1-butanol at 298.15 K), 1-butyl-3-methylimidazolium methylsulfate, [BMIM][CH3SO4] in alcohol (methanol, or ethanol, or 1-butanol at 298.15 K), 1-butyl-3-methylimidazolium octylsulfate, [BMIM][OcSO4] in alcohol (methanol, or 1-butanol at 298.15 K) and of 1-hexyloxymethyl-3-methylimidazolium tetrafluoroborate, [C6H(13)OCH2MIM][BF4], 1,3-dihexyloxymethylimidazolium tetrafluoroborate, [(C6H13OCH2)2IM][BF4] in alcohol (methanol, or 1-butanol, or 1-hexanol at 308.15 and 318.5 K) and hexyl(2-hydroxyethyl)dimethylammonium bromide, C6Br in 1-octanol at 298.15 K. The set of ammonium ionic liquids of different cations and anions (C2Br, C2BF4, C2PF6, C2N(CN)2, C3Br, C4Br and C6Br) was chosen to show the influence of small amount of the ammonium ionic liquid on the surface tension of water at 298.15 K. The influence of the cation, or anion alkyl chain length on the properties under study (densities and surface tension) was tested.  相似文献   

13.
采用水溶性三(间-磺酸钠苯基)膦(TPPTS)作稳定剂, 在离子液体1-丁基-3-甲基-咪唑四氟硼酸盐([BMIM]BF4)或1-丁基-3-甲基-咪唑对甲基苯磺酸盐([BMIM][p-CH3C6H4SO3])介质中用氢气还原RuCl3·3H2O, 得到钌纳米粒子. 将此钌纳米粒子与(1S, 2S)-1,2-二苯基乙二胺(简称(1S, 2S)-DPEN)、KOH在离子液体/异丙醇介质中原位生成一种不对称加氢催化剂, 用于催化苯乙酮及其衍生物的不对称加氢反应. 实验结果表明, 离子液体介质中的纳米钌催化剂体系具有良好的催化活性和对映选择性. 在优化反应条件下, 催化苯乙酮获得了100%的转化率和79.1%的对映选择性. 并且产物经正己烷萃取后, 含有钌纳米粒子的离子液体可以循环使用.  相似文献   

14.
Eight common dialkylimidazolium-based ionic liquids have been successfully evaporated in ultra-high vacuum and their vapours analysed by line of sight mass spectrometry using electron ionisation. The ionic liquids investigated were 1-alkyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide, [C(n)C(1)Im][Tf(2)N] (where n = 2, 4, 6, 8), 1-alkyl-3-methylimidazolium tetrafluoroborate, [C(n)C(1)Im][BF(4)] (where n = 4, 8), 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)] and 1-butyl-3-methylimidazolium tetrachloroferrate, [C(4)C(1)Im][FeCl(4)]. All ionic liquids studied here evaporated as neutral ion pairs; no evidence of decomposition products in the vapour phase were observed. Key fragment cations of the ionised vapour of the ionic liquids are identified. The appearance energies, E(app), of the parent cation were measured and used to estimate the ionisation energies, E(i), for the vapour phase neutral ion pairs. Measured ionisation energies ranged from 10.5 eV to 13.0 eV. Using both the identity and E(app) values, the fragmentation pathways for a number of fragment cations are postulated. It will be shown that the enthalpy of vaporisation, Δ(vap)H, can successfully be measured using more than one fragment cation, although caution is required as many fragment cations can also be formed by ionisation of decomposition products.  相似文献   

15.
A novel strategy for tailoring the adsorption and structural properties of ionic liquid derived carbons has been developed. By changing the carbonization temperature and ratios of ionic liquids (ILs) containing a cross-linkable anion, such as 1-butyl-3-methylimidazolium tricyanomethanide [BMIm][C(CN)(3)] and 1-ethyl-3-methylimidazolium tetracyanoborate [EMIm][B(CN)(4)], boron and nitrogen-rich carbons with slit-like pores and specific surface areas exceeding 500 m(2) g(-1) have been prepared. Furthermore, the nitrogen-rich carbons exhibit high adsorption capacity for CO(2) adsorption and selectivity for CO(2)/N(2) separation.  相似文献   

16.
The enthalpies of vaporisation, Δ(vap)H(298), of seven ionic liquids (ILs) (four imidazoliums, a pyridinium, a phosphonium and an isouronium) have been determined by temperature programmed desorption using line of sight mass spectrometry. They were: 1-ethyl-3-methylimidazolium bis(pentafluoroethyl)phosphinate, [C(2)C(1)Im][PO(2)(C(2)F(5))(2)]; 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)]; 1-butyl-3-methylimidazolium tetrafluoroborate, [C(4)C(1)Im][BF(4)]; 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C(6)C(1)Im][FAP]; 1-butylpyridinium methylsulfate, [C(4)Py][C(1)OSO(3)]; trihexyl(tetradecyl)phosphonium tetrafluoroborate, [P(6,6,6,14)][BF(4)] and O-ethyl-N,N,N',N'-tetramethylisouronium trifluoromethanesulfonate, [C(2)(C(1))(4)iU][TfO]. The values were found to be consistent with a previously proposed, predictive, model in which Δ(vap)H(298) is decomposed into a Coulombic component (computable from the IL density) and van der Waals components from the anion and cation. Two previously predicted values of Δ(vap)H(298) were found to be within 6 kJ mol(-1) of the measured experimental values. Values for the van der Waals components are tabulated for eleven cations and twelve anions. Predictions are made for Δ(vap)H(298) for 13 ILs with as yet unmeasured Δ(vap)H(298) values (using experimental molar volumes), and for a further 44 ILs using estimated molar volumes.  相似文献   

17.
Journal of Solution Chemistry - For three binary mixtures composed of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with 2-propanol, N,N?dimethylacetamide (DMA) and...  相似文献   

18.
We compare how (i) four ionic liquids (ILs) (1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpy][Tf2N]), and trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P(C6)3C14][Tf2N])) and (ii) two conventional molecular liquids (methanol and 1-octanol) solvate/wet luminescent organic moieties that are covalently attached to the surface of silica controlled pore glass (CPG). A series of aminopropyl CPG particles that have been covalently tagged with the solvatochromic fluorescent probe group dansyl were used in this study. The results demonstrate that ILs solvate/wet the silica surface differently in comparison to molecular liquids (MLs). Specifically, when comparing ILs and MLs that appear to solvate the free probe, dansylpropylsulfonamide (DPSA), equally in solution, we find that ILs do not solvate/wet the silica surfaces as well as the corresponding MLs. The cation component in these ILs is the significant factor in how the ILs solvate/wet silica surfaces. Solvation/wetting of surface-bound species at a silica surface depends on the cation size. Chlorosilane end-capping of the surface silanol and amine residues attenuates the cation's affects.  相似文献   

19.
Sound velocity is determined by the transient grating method in a range from 10(6) to 10(10) Hz in three room temperature ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, and N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide. In all room temperature ionic liquids studied, the sound velocity increased with increasing frequency. The cause of this change is posited to be structural relaxation in the room temperature ionic liquids. Frequency dependence of the sound velocity is not reproduced by a simple Debye relaxation model. The sound velocity dispersion relation in 1-butyl-3-methylimidazolium hexafluorophosphate matches a Cole-Davidson function with parameters determined by a dielectric relaxation [C. Daguenet et al., J. Phys. Chem. B 110, 12682 (2006)], indicating that structural and reorientational relaxations are strongly coupled. Conversely, the sound velocity dispersions of the other two ionic liquids measured do not match those measured for dielectric relaxation, implying that structural relaxation is much faster than the reorientational relaxation. This difference is discussed in relation to the motilities of anions and cations.  相似文献   

20.
The steady-state fluorescence spectra and molecular dynamics simulations were explored to investigate the temperature dependent organization in some imidazolium ionic liquids:1-butyl-3-methylimidazolium hexafluo-rophosphate([bmim][PF6]),1-ethyl-3-methylimidazolium ethylsulfate([emim][EtSO4]) and 1-butyl-3-methylimida-zolium tetrafluoroborate([bmim][BF4]).The pure room temperature ionic liquids(ILs) exhibit a large red shift at more than an excitation wavelength of around 340 nm,which demonstrates the hetero...  相似文献   

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