共查询到20条相似文献,搜索用时 52 毫秒
1.
Towards the Application of Structure–Property Relationship Modeling in Materials Science: Predicting the Seebeck Coefficient for Ionic Liquid/Redox Couple Systems
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Anita Sosnowska Maciej Barycki Dr. Agnieszka Gajewicz Dr. Maciej Bobrowski Dr. Sylwia Freza Prof. Piotr Skurski Stefanie Uhl Edith Laux Tony Journot Laure Jeandupeux Prof. Herbert Keppner Dr. Tomasz Puzyn 《Chemphyschem》2016,17(11):1591-1600
This work focuses on determining the influence of both ionic‐liquid (IL) type and redox couple concentration on Seebeck coefficient values of such a system. The quantitative structure–property relationship (QSPR) and read‐across techniques are proposed as methods to identify structural features of ILs (mixed with LiI/I2 redox couple), which have the most influence on the Seebeck coefficient (Se) values of the system. ILs consisting of small, symmetric cations and anions with high values of vertical electron binding energy are recognized as those with the highest values of Se. In addition, the QSPR model enables the values of Se to be predicted for each IL that belongs to the applicability domain of the model. The influence of the redox‐couple concentration on values of Se is also quantitatively described. Thus, it is possible to calculate how the value of Se will change with changing redox‐couple concentration. The presence of the LiI/I2 redox couple in lower concentrations increases the values of Se, as expected. 相似文献
2.
Francesco Greco Dr. Sunghwan Shin Prof. Dr. Federico J. Williams Bettina S. J. Heller Dr. Florian Maier Prof. Dr. Hans-Peter Steinrück 《ChemistryOpen》2019,8(12):1365-1368
A new approach to investigate potential screening at the interface of ionic liquids (ILs) and charged electrodes in a two-electrode electrochemical cell by in situ X-ray photoelectron spectroscopy has been introduced. Using identical electrodes, we deduce the potential screening at the working and the counter electrodes as a function of applied voltage from the potential change of the bulk IL, as derived from corresponding core level binding energy shifts for different IL/electrode combinations. For imidazolium-based ILs and Pt electrodes, we find a significantly larger potential screening at the anode than at the cathode, which we attribute to strong attractive interactions between the imidazolium cation and Pt. In the absence of specific ion/electrode interactions, asymmetric potential screening only occurs for ILs with different cation and anion sizes as demonstrated for an imidazolium chloride IL and Au electrodes, which we assign to the different thicknesses of the electrical double layers. Our results imply that potential screening in ILs is mainly established by a single layer of counterions at the electrode. 相似文献
3.
Radha G. Bhuin Leonhard Winter Matthias Lexow Florian Maier Hans‐Peter Steinrück 《Angewandte Chemie (International ed. in English)》2020,59(34):14429-14433
The impact of a reactant from the gas phase on the surface of a liquid and its transfer through this gas/liquid interface are crucial for various concepts applying ionic liquids (ILs) in catalysis. We investigated the first step of the adsorption dynamics of n‐butane on a series of 1‐alkyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide ILs ([CnC1Im][Tf2N]; n=1, 2, 3, 8). Using a supersonic molecular beam in ultra‐high vacuum, the trapping of n‐butane on the frozen ILs was determined as a function of surface temperature, between 90 and 125 K. On the C8‐ and C3‐ILs, n‐butane adsorbs at 90 K with an initial trapping probability of ≈0.89. The adsorption energy increases with increasing length of the IL alkyl chain, whereas the ionic headgroups seem to interact only weakly with n‐butane. The absence of adsorption on the C1‐ and C2‐ILs is attributed to a too short residence time on the IL surface to form nuclei for condensation even at 90 K. 相似文献
4.
通过溶胶-凝胶法制备了硅胶包载咪唑类离子液体修饰电极,研究其与体相离子液体不同的伏安行为;另一方面,制备不同离子液体含量为15% ~ 28%的包载离子液体硅胶和涂覆离子液体硅胶,用电化学阻抗研究其在20 oC到80 oC下电导率的变化情况. 异常的电化学行为主要表现在:1)硅胶包载离子液体导致Fc/Fc+电对的半波电位正移63.5 ~ 200 mV;2)当离子液体限域于硅胶纳米孔道中时,离子液体的电化学稳定性变差;3)包载离子液体硅胶的电导率要比涂覆离子液体的电导率高29.6% ~ 136%. 由此推断,可能是由于离子液体充满硅胶孔腔和孔道从而形成了纳米网状的离子液体导电介质. 这些结果表明,硅胶包载离子液体不仅可以作为修饰电极的优良载体,而且也有助于理解离子液体限域于硅胶纳米孔道中的限域效应. 相似文献
5.
Qingbo Li Jingyun Jiang Guofeng Li Wancheng Zhao Xinhui Zhao Tiancheng Mu 《中国科学:化学(英文版)》2016,59(5):571-577
Room temperature ionic liquids (ILs) composed of cations and anions, as well as deep eutectic solvents (DESs) composed of hydrogen bond donors (HBDs) and hydrogen bond acceptors (HBAs), are regarded as green solvents due to their low volatility. They have been used widely for electrochemically driven reactions because they exhibit high conductivity and excellent electrochemical stability. However, no systematic investigations on the electrochemical potential windows (EPWs), which could be used to characterize the electrochemical stability, have been reported. In this regard, the EPWs of 33 ILs and 23 DESs have been studied utilizing cyclic voltammetry (CV) method and the effects of structural factors (cations and anions of ILs, and HBDs and HBAs of DESs) and external factors (electrode, water content) on the EPWs have been comprehensively investigated. The electrochemical stability of selected ILs comprising five traditional cations, namely imidazolium, pyridinium, pyrrolidinium, piperidinium and ammonium and 13 kinds of versatile anions was studied. The results show that for ILs, both cation and anion play an important role on the reductive and oxidative potential limit. For a same IL at different working electrode, for example, glassy carbon (GC), gold (Au) and platinum (Pt) electrode, the largest potential window is almost observed on the GC working electrode. The investigations on the EPWs of choline chloride (ChCl), choline bromide (ChBr), choline iodide (ChI), and methyl urea based DESs show that the DES composed of ChCl and methyl urea has the largest potential window. This work may aid the selection of ILs or DESs for use as a direct electrolyte or a solvent in electrochemical applications. 相似文献
6.
本文将经水蒸气二次活化的椰壳活性炭(W-AC)作为电极材料,选择1-乙基-3甲基咪唑四氟硼酸盐([EMIM]BF4)作为电解质,结果表明W-AC电极的比电容量远高于未活化的椰壳活性炭(R-AC).使用循环伏安、恒电流充放电、交流阻抗等方法研究了不同种类离子液体电解质对超级电容器电化学性能的影响.不同阴阳离子组成的离子液体作为电解质,直接影响超级电容器的电化学性能. 研究表明,由EMIM+和BMIM+阳离子与BF4-、TFSI-阴离子构成的离子液体电解质较适用于W-AC电极. 其中在[EMIM]BF4电解质中,单片电极的比电容量可高达153 F·g-1;在1-丁基-3-甲基-咪唑四氟硼酸盐([BMIM]BF4)电解质中电位窗可达3.5V,能量密度可高达57 Wh·kg-1.本研究对于构筑高性能超级电容器离子液体的选择提供参考,以满足不同应用领域需求. 相似文献
7.
Vapor pressures of six aqueous lithium nitrate solutions with molalities of (0.181, 0.526, 0.963, 1.730, 2.990, and 5.250) mol-kg–1 have been measured in the temperature range 423.15–623.15 K with a constant-volume piezometer immersed in a precision liquid thermostat. The static method was used to measure the vapor pressure. The total uncertainty of the temperature, pressure and composition measurements were estimated to be less than 15 mK, 0.2%, and 0.014%, respectively. The vapor pressures of pure water were measured with the same apparatus and procedure to confirm the accuracy of the method used for aqueous lithium nitrate solutions. The results for pure water were compared with high-accuracy PS–TS data calculated from the IAPWS standard equation of state. Important thermodynamic functions (activities of water and lithium nitrate, partial molar volumes, osmotic coefficient, excess relative partial molar entropy, and relative partial molar enthalpy values of the solvent) were derived using the measured values of vapor pressure for the solution and pure water. The measured and derived thermodynamic properties for solutions were compared with data reported in the literature. The present results are consistent with most previous reported thermodynamic data for the pure water and H2O + LiNO3 solutions at low temperatures. 相似文献
8.
Influence of different alkyl‐methylimidazolium tetrafluoroborate ionic liquids on the structure of pebax® films. Consequences on thermal,mechanical, and water sorption and diffusion properties
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Sylvain Magana Olivier Gain Fabrice Gouanvé Eliane Espuche 《Journal of Polymer Science.Polymer Physics》2016,54(8):811-824
In this work, three ionic liquids (ILs) differing by the length of the alkyl chain linked to their cation were incorporated in a Pebax® copolymer matrix through a solvent cast process for composition from 0 to 70 wt % IL. The copolymer/IL miscibility was investigated via IR Spectroscopy, Differential Scanning Calorimetry and Scanning Electron Microscopy. The three ILs dissolved in the copolymer soft phase for ILs content below 30 wt % whereas they formed segregated dispersed domains at higher loadings. The plasticizing effect of the ILs was examined through DSC and thermomechanical analyses. In the range of IL amount from 0 to 30 wt %, no significant differences were observed in the thermomechanical properties as a function of the IL structure. At higher IL content, the films based on 1‐ethyl‐methylimidazolium tetrafluoroborate sustained better properties. All films exhibited a good thermal stability up to 300 °C. The water sorption isotherms were modeled with GAB equation and both the kinetic and thermodynamic parameters of the sorption mechanism were investigated. A non‐monotonic evolution of the GAB parameters and diffusion coefficient as a function of the IL content was evidenced. Moreover, different behaviors were observed as a function of the IL nature and structuration within the copolymer matrix. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 811–824 相似文献
9.
The oxidative electrochemistry of cymantrene, CpMn(CO)3 (1; Cp = [η5-C5H5]–), was examined in ionic liquids (ILs) composed of anions of varying Lewis base properties. It was observed that the cyclic voltammetric responses strongly depended on the nucleophilic properties of the IL anion. Still, all observations are consistent with the initial formation of 1+ followed by an attack from the IL anion. In bis(trifluoromethylsulfonyl)amide [NTf2]-based ILs, the process shows close to ideal electrochemical reversibility as the reaction between 1+ and [NTf2] anion is very slow. On the other hand, in tetrafluoroborate and trifluoromethanesulfonate-based IL, the oxidation of 1 shows different levels of electrochemical reversibility with a marked sign of anion attack to 1+. In contrast, 1 exhibits an irreversible oxidation process in hexafluorophosphate-based IL. The reaction rate constants for the interaction of 1+ with the different IL anions were estimated by fitting the experimental data to digital simulations of the proposed mechanism. Besides, the use of [NTf2]-based ILs as a supporting electrolyte in CH2Cl2 was also examined. The oxidation process of 1 shows a close to ideal electrochemical reversibility but low to non-chemical reversibility. This study illustrates the wide range of electrochemical environments available with ILs and demonstrates their limited utility for investigating the redox properties of metal carbonyl compounds. It also intends to warn the reader on how the IL media may influence an electrochemical study if care is not exercised. 相似文献
10.
Rezaei Behzad Havakeshian Elaheh Hajipour Abdol R. 《Journal of Solid State Electrochemistry》2011,15(2):421-430
The aim of this study is to introduce the application of some acidic ionic liquids (ILs) as an electrolyte additive in lead-acid
batteries. A family of alkylammonium hydrogen sulfate ILs, which are different in the number of alkyl chain, is investigated
with the aim to compare their effects on the electrochemical behavior of Pb–Sb–Sn alloy in sulfuric acid solution. The hydrogen
and oxygen gas evolution potential and anodic layer characteristics were investigated employing cyclic and linear sweep voltammetric
methods. The morphological changes of the PbSO4 layer that formed on the electrode surface were confirmed using scanning electron microscopy. Also, potentiodynamic polarization
curves, electrochemical impedance spectroscopy, and an equivalent circuit analysis were used to evaluate the corrosion behaviors
of the Pb–Sb–Sn alloy in the presence of ILs. The obtained results indicate that hydrogen and oxygen evolution overpotential
of lead–antimony–tin alloy increases in the solution containing IL and mainly depends on the number of alkyl chain in alkylammonium
cation. It is clearly observed that the morphology of PbSO4 layer changes under the influence of ILs. The corrosion studies show an increase in corrosion resistance of lead alloy in
the presence of some ILs. Also, the electrochemical effects of ILs in conversion of PbSO4 to PbO2 and vice versa were investigated by carbon-PbO paste electrode. Cyclic voltammogram of carbon-PbO electrode shows that in
the presence of ILs, oxidation and reduction peak currents increase, while reversibility decreases. 相似文献
11.
Ana B. Pereiro Helena I.M. Veiga José M.S.S. Esperança Ana Rodríguez 《The Journal of chemical thermodynamics》2009,41(12):1419-1423
Density, speed of sound, refractive index, and dynamic viscosity of the ionic liquids (ILs) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, BMpyr NTf2, and trihexyl(tetradecyl) phosphonium dicyanamide, P66614 dca, were studied as a function of temperature at atmospheric pressure. Thermal expansion coefficient, αp, molecular volumes, and standard entropies of these ILs were calculated from the experimental density values. The solubility of three aromatic components (benzene, toluene, and ethylbenzene) in the selected ILs was carried out at T = 298.15 K and atmospheric pressure and compared with literature values for sulfolane. 相似文献
12.
Dr. Ulrich Preiss Dr. Vladimir N. Emel'yanenko Prof. Dr. Sergey P. Verevkin Dr. Daniel Himmel Dr. Yauheni U. Paulechka Prof. Dr. Ingo Krossing 《Chemphyschem》2010,11(16):3425-3431
Modeling of the temperature‐dependent liquid entropy of ionic liquids (ILs) with great accuracy using COSMO‐RS is demonstrated. The minimum structures of eight IL ion pairs are investigated and the entropy, calculated from ion pairs, is found to differ on average only 2 % from the available experimental values (119 data points). For calculations with single ions, the average error amounts to 2.6 % and stronger‐coordinating ions tend to give higher deviations. Additionally, the first parameterization of the standard liquid entropy for ILs is presented in the context of traditional volume‐based thermodynamics (Sl0=1.585 kJ mol?1 K?1 nm?3?rm3+14.09 J mol?1 K?1), which sheds light on the statistical treatment of ionic interactions. The findings provide the first direct access to accurate predictions of liquid entropies of ILs, which are tedious and time‐consuming to measure. 相似文献
13.
Renxiong Li Juehan Yang Nengjie Huo Chao Fan Fangyuan Lu Tengfei Yan Dr. Zhongming Wei Prof. Jingbo Li 《Chemphyschem》2014,15(12):2510-2516
Bi2S3 single‐crystalline nanowires are synthesized through a hydrothermal method and then fabricated into single nanowire photodetectors. Due to the different contact barrier between the gold electrode and Bi2S3 nanowires, two kinds of devices with different electrical contacts are obtained and their photoresponsive properties are investigated. The non‐ohmic contact devices show larger photocurrent gains and shorter response times than those of ohmic contact devices. Furthermore, the influence of a focused laser on the barrier height between gold and Bi2S3 is explored in both kinds of devices and shows that laser illumination on the Au?Bi2S3 interface can greatly affect the barrier height in non‐ohmic contact devices, while keeping it intact in ohmic contact devices. A model based on the surface photovoltage effect is used to explain this phenomenon. 相似文献
14.
Yiting Chen Xiaoping Chen Zhenyu Lin Hong Dai Bin Qiu Jianjun Sun Lan Zhang Guonan Chen 《Electrochemistry communications》2009,11(6):1142-1145
A heated composite electrode consisted of multi-wall carbon nanotube (MWNT) and ionic liquids (ILs) was designed and fabricated. The non-conductive binders were replaced by a conductive IL, n-octylpyridinum hexafluorophosphate (OPFP). This heated OPFP/MWNT composite electrode was applied for electrochemiluminescent (ECL) sensor, and the performance of ECL sensor was evaluated by ascorbic acid (AA)/lucigenin ECL system. The new heated electrode combines the advantages of ILs/CNT and heated electrode, showing high thermal stability and conductivity, simple heating setups, improved reproducibility, renewable surface, simplicity of fabrication and enhanced sensitivity with detection limit (S/N = 3) of 0.01 μmol/L for AA. 相似文献
15.
Huiyong Wang Jianji Wang Prof. Dr. Sheli Zhang Yuanchao Pei Dr. Kelei Zhuo Prof. Dr. 《Chemphyschem》2009,10(14):2516-2523
Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [Cnmim]Br (n=4, 6, 8, 10, 12), [C4mim][BF4], and [C4mim][PF6] in various molecular solvents (water, methanol, 1‐propanol, 1‐pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee–Wheaton conductivity equation in terms of the ionic association constant (KA) and the limiting molar conductance (Λm0). Combined with the values for the Br? anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF4]? and [PF6]? anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br?), the Λm0 values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the KA values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C4mim]+ cation, the limiting molar conductivities of the ILs decrease in the order Br?>[BF4]?>[PF6]?, and their ionic association constants follow the order [BF4]?>[PF6]?>Br? in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln KA of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents. 相似文献
16.
Morphology of Imidazolium‐Based Ionic Liquids as Deposited by Vapor Deposition: Micro‐/Nanodroplets and Thin Films
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. José C. S. Costa Prof. Adélio Mendes Prof. Luís M. N. B. F. Santos 《Chemphyschem》2016,17(14):2123-2127
The morphology of micro‐ and nanodroplets and thin films of ionic liquids (ILs) prepared through physical vapor deposition is presented. The morphology of droplets deposited on indium‐tin‐oxide‐coated glass is presented for the extended 1‐alkyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([CnC1im][Ntf2]; n=1–8) series, and the results show the nanostructuration of ILs. The use of in‐vacuum energetic particles enhances/increases the nanodroplets mobility/coalescence mechanisms and can be a pathway to the fabrication of thin IL films. 相似文献
17.
Laforge FO Kakiuchi T Shigematsu F Mirkin MV 《Journal of the American Chemical Society》2004,126(47):15380-15381
The rates of electron transfer (ET) reactions at the water/ionic liquid (IL) interface have been measured for the first time using scanning electrochemical microscopy. The standard bimolecular rate constant of the interfacial ET between ferrocene dissolved in 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and aqueous ferricyanide (0.4 M-1 cm s-1) was found to be approximately 30 times higher than the corresponding rate constant measured at the water/1,2-dichloroethane interface. The driving force dependence of the ET rate was investigated over a wide range of the interfacial potential drop values (>200 mV). The observed Butler-Volmer-type dependence is discussed in terms of the interfacial model. The ET was also probed at the interface between aqueous solution and the mixture of the IL and 1,2-dichloroethane. The mole fractions in this mixture were varied systematically to investigate the transition from the water/organic to the water/IL interface. The observed decrease in the rate constant with increasing mole fraction of 1,2-dichloroethane is in contrast with the previously reported direct correlation between the electrochemical rate constant and the diffusion coefficient of redox species in solution. 相似文献
18.
《Electrochemistry communications》2007,9(7):1567-1572
Ionic liquids (IL) are very promising “solvent-free” electrolytes for high-voltage double-layer supercapacitors (EDLCs) and to this purpose they are generally selected on the basis of their bulk properties, such as electrochemical stability and ion conductivity, without taking into account those of the electrified electrode-IL interface. This interface, which has yet to be well characterized, has features that notably affect electrode capacitance, and our paper for the first time highlights the importance of the molecular chemistry and structure of the ions for the double-layer capacitive response of carbonaceous electrodes in IL. The double-layer capacitive responses of negatively charged electrodes based on activated carbons and aero/cryo/xerogel carbons in two ILs featuring the same anion and different cations of almost the same size, i.e. the N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) and 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) are reported. The porosity, structure and surface chemistry of the carbons are compared to their capacitive response to evince the role played by these carbon properties and by the chemistry and structure of the IL ions in the electric double-layer. 相似文献
19.
Qin Qian Ping Yu Hanjun Cheng Xiang Wang Lifen Yang Lanqun Mao 《Electroanalysis》2011,23(12):2870-2877
Quantification of hygroscopicity of ionic liquids (ILs) is of great importance in both fundamental studies and practical applications of ILs. This study demonstrates an electrochemical method for effectively quantifying the hygroscopicity of ILs through electrochemically monitoring water contents absorbed into ILs. The measurements of water content absorbed into the ILs are performed with square wave voltammetry (SWV) based on the water‐induced enhancement of diffusion of solution‐dissolved potassium ferricyanide (K3Fe(CN)6) redox probe. For demonstration, two kinds of ILs with different hygroscopicity (i.e., hydrophilic Bmim+Gly? and hydrophobic Bmim+PF6?) are employed in this study. The dissolution of K3Fe(CN)6 redox probe into ILs is found to have little effect on the hygroscopicity of ILs. The hygroscopicity of ILs is thus able to be quantified by monitoring water content absorbed into ILs as a function of time when ILs are stored at room temperature and standard atmospheric pressure under 55 % relative humidity (RH). Under the conditions employed in this study, the hygroscopicity of Bmim+Gly? and Bmim+PF6? is determined to be 1.33 M per hour and 0.05 M per hour, respectively, which are almost consistent with those measured with Karl Fischer titration under the same conditions. The electrochemical method demonstrated in this study is experimentally simply and environmentally benign and may be potentially extended for general quantification of hygroscopicity of ILs. 相似文献
20.
Sheying Dong Nan Li Penghui Zhang Yunsheng Li Zhen Chen Tinglin Huang 《Electroanalysis》2012,24(7):1554-1560
A novel H2O2 amperometric biosensor based on the electrodeposition of gold nanoparticles (AuNPs) and CdS quantum dots (CdS QDs) onto a carbon paste electrode (CPE) and immobilizing hemoglobin (Hb) with ionic liquid (IL), is presented in this article. The modification process of the electrode was monitored by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to synergistic effects of AuNPs, CdS QDs and IL, the biosensor exhibited high stability and good bioelectrocatalytic ability to H2O2 with a linear concentration range from 10 to 750 µM and a detection limit of 4.35 µM (S/N=3). 相似文献