Kinetics of ion transfer at the ionic liquid/water nanointerface

Ion transfer (IT) processes in ionic liquids (ILs) are essential for their applications in electrochemical systems and chemical separations. In this Article, the first measurements of IT kinetics at the IL/water interface are reported. Steady-state voltammetry was performed at the nanometer-sized polarizable interface between water and ionic liquid, [THTDP(+)][C(4)C(4)N(-)], immiscible with it that was formed at the tip of a nanopipet. Kinetic measurements at such interfaces are extremely challenging because of slow mass-transfer rates in IL, which is ～700 times more viscous than water. The recently developed new mode of nanopipet voltammetry, common ion voltammetry, was used to overcome technical difficulties and ensure the reliability of the extracted kinetic parameters of IT. The results suggest that the rate of interfacial IT depends strongly on solution viscosity. Voltammetric responses of nanopipets of different radii were analyzed to evaluate the effect of the electrical double layer at the liquid/liquid interface on IT kinetics. The possibility of the influence of the charged pipet wall on ion transport was investigated by comparing currents produced by cationic and anionic species. Possible effects of relaxation phenomena at the IL/water interface on IT voltammograms have also been explored.     

Comparative study of electron transfer reactions at the ionic liquid/water and organic/water interfaces

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.     

Investigation of the oxidation of hydroquinone at the liquid/liquid interface

<正>The oxidation of hydroquinone(QH_2) was investigated for the first time at liquid/liquid(L/L) interface by scanning electrochemical microscopy(SECM).In this study,electron transfer(ET) from QH_2 in aqueous to ferrocene(Fc) in nitrobenzene (NB) was probed.The apparent heterogeneous rate constants for ET reactions were obtained by fitting the experimental approach curves to the theoretical values.The results showed that the rate constants for oxidation reaction of QH_2 were sensitive to the changes of the driving force,which increased as the driving force increased.In addition,factors that would affect ET of QH_2 were studied.Experimental results indicated ion situation around QH_2 molecule could change the magnitude of the rate constants because the capability of oxidation of QH_2 would be affected by them.     

应用扫描电化学显微镜研究极化液/液界面上的电子转移反应

将含有氧化还原电对的水溶液滴涂在铂盘电极表面, 然后将该电极插入到1,2-二氯乙烷溶液中, 形成稳定的油/水界面. 液滴中的K3Fe(CN)6和K4Fe(CN)6氧化还原电对既可以作为水相中的参比电对参与控制液/液界面上的电势差, 同时又可以作为水相的电子授受体参与界面上的电子转移反应. 结合扫描电化学显微镜电化学系统的特点, 利用其双恒电位仪分别控制界面电势差和现场扫描的优点, 通过扫描电化学显微镜的渐进曲线得到了不同界面电势差控制的电子转移反应速率常数. 实验结果表明, 应用此方法获得的液/液界面可以被外加电位极化, 在一定的电势差范围内, 反应速率常数与界面电势差的关系遵守Butler-Volmer公式.     

Observation of the marcus inverted region of electron transfer reactions at a liquid/liquid interface

Scanning electrochemical microscopy was used to probe the influence of a driving force on the heterogeneous electron transfer (ET) processes at the externally polarized water/1,2-dichloroethane interface. Being a part of the driving force, the Galvani potential difference at the interface, Deltaowphi, can be quantitatively controlled in a wide range, allowing the precise measurements of the rate constants of the ET reactions. Two opposite systems were chosen in this work. One was 5,10,15,20-tetraphenyl 21H,23H-porphyrin zinc (ZnPor, O)/Fe(CN)64- (W), and the other was TCNQ (O)/Fe(CN)63- (W). For both systems studied, the relations between the rate constant and the Deltaowphi were of parabolic shape; that is, the rate constants increased initially with the Deltaowphi until reaching a maximum and then decreased steadily as the Deltaowphi increased further. This is in accordance with the prediction of the Marcus theory. To our knowledge, this is the first report that the Marcus inverted region can be observed electrochemically at an unmodified liquid/liquid interface with only one redox couple at each phase. The effect of the concentrations of the organic supporting electrolyte has also been discussed in detail.     

Heterogeneous electron transfer at Au/SAM junctions in a room-temperature ionic liquid under pressure

Proven electrochemical approaches were applied to study heterogeneous electron transfer (ET) between selected redox couples and gold electrodes modified with alkanethiol self-assembled monolayers (SAMs), using the room-temperature ionic liquid (RTIL) [bmim][NTf2] as reaction medium; ferrocene as freely diffusing redox probe in the RTIL was tested for ET through both thin (butanethiol) and thick (dodecanethiol) assemblages at pressures up to 150 MPa; well behaved kinetic patterns and reproducibility of data were demonstrated for ET within the unique Au/SAM/RTIL arrays.     

Solvated CH5+ in liquid superacid

The transition states for methane activation in liquid superacid have been studied by experimentally determined secondary kinetic deuterium isotope effects (SKIEs) and computational chemistry. For the first time, the SKIEs on hydrogen/deuterium exchange of methane have been measured by using the methane isotopologues in homogeneous liquid superacid (2HF/SbF5). To achieve high accuracy of the SKIEs, the rate constants for pairs of methane isotopologues were simultaneously measured in the same superacid solution by using NMR spectroscopy. Density functional theory (DFT) and high-level ab initio methods have been employed to model possible intermediates and transition states, assuming that the superacids involved in the exchange reactions are H2F+ ions solvated by HF. Only the unsolvated superacid H2F+ is found to be strong enough to protonate methane, yielding the methonium ion solvated by HF as a potential energy minimum. In contrast, the (HF)x-solvated H2F+ superacids (x = 1-4) do not appear to be strong enough to yield stable solvated methonium ions. However, such ions show up as parts of the transition states of the exchange in which the methonium ions are solvated by (HF)x. The calculated DFT activation barrier is in good agreement with that experimentally observed.     

A novel method for dynamic investigations of photoinduced electron transport using functionalized-porphyrin at ITO/liquid interface

A new scanning electrochemical microscopy (SECM) model provided a two-dimensional quantitative analysis on a heterogeneous electron transport (ET) process of a functionalized porpyrin by photoinduced ET at the ITO/liquid interface. The basic features of oxidized porphyrin under light source were recorded by feedback approach curves within the framework of the bimolecular ET mechanisms.     

Evidence for ionic samarium(II) species in THF/HMPA solution and investigation of their electron-donating properties

The fundamental nature of samarium(II) complexes in THF/HMPA (HMPA = hexamethylphosphoramide) solutions containing SmI2 has been clarified by means of cyclic voltammetry, conductivity measurements, UV spectroscopy, and kinetic measurements. The principal species is not [SmI2(hmpa)4] as previously suggested, but either the ionic cluster [Sm(hmpa)4(thf)2+2I- if four equivalents of HMPA is present in the THF solution or [Sm(hmpa)6]2+ 2I- in the presence of at least 10 equivalents of HMPA. The formal potential of the [Sm(hmpa)4(thf)2]3+ 2I-/[Sm(hmpa)4(thf)2]2- 2I- redox couple determined by cyclic voltammetry was -1.79 +/- 0.08 V versus SCE. The order of reactivity of the samarium(II) complexes was found to be [Sm(hmpa)6]2+2I- > [Sm(hmpa)4(thf)2]2+2I- > SmI2 in their respective reactions with 1-iodobutane and with benzyl chloride. Very high rate enhancements, of the order of 1,000-15,000-fold, were observed upon addition of HMPA to the THF solution containing SmI2, Comparison of these rate constants with the corresponding rate constants for electron transfer (ET) reactions involving aromatic radical anions revealed that none of the reactions studied can be classified as outer-sphere ET processes and that the inner-sphere electron-donating abilities of the [Sm(hmpa)4(thf)2]2+ 2I- and SmI2 complexes are comparable. The inner-sphere ET character of the transition state increases on going from 1-iodobutane and benzyl bromide to benzyl chloride and acetophenone.     

The diffusion coefficient of H2S in liquid sulfur

The diffusion coefficient of H₂S in liquid sulfur is a key kinetic parameter that has been missing in literature. In this paper, a pressure decay method was applied to measure the diffusion coefficients of H₂S in liquid sulfur at 403 and 423 K. This pressure decay process was then modeled by taking the simultaneous diffusion and reversible chemical reactions between H₂S and liquid sulfur into consideration. The diffusion coefficients and reaction rate constants were numerically determined by fitting theoretical curves to experimental data using Finite Element Method and Genetic Algorithm. The solubility of H₂S in liquid sulfur at 403 and 423 K was also calculated and the results agreed with the semi-empirical correlation lately reported in literature. This study further extended the validity of the correlation to higher partial H₂S pressure conditions.     

Isomerization of cyclic hydrocarbons mediated by an AlCl3-based ionic liquid as catalyst

Cyclohexane and methylcyclopentane isomerization were carried out under mild conditions using an ionic liquid consisting of n-butylpyridinium chloride and aluminum chloride as catalyst. The ionic liquid showed reasonably high catalytic activity in both reactions with a selectivity to corresponding products of 100%. In the case of cyclohexane isomerization, the thermodynamic equilibrium methylcyclopentane ⇌cyclohexane was almost achieved. For the reaction of cyclohexane isomerization, the kinetic study was performed, and the rate constants and the activation energy of the process were determined. This revised version was published online in June 2006 with corrections to the Cover Date.     

Transport of redox probes through single pores measured by scanning electrochemical-scanning ion conductance microscopy (SECM-SICM)

We report scanning electrochemical microscopy-scanning ion conductance microscopy (SECM-SICM) experiments that describe transport of redox active molecules which emanate from single pores of a track-etch membrane. Experiments are performed with electrodes which consist of a thin gold layer deposited on one side of a nanopipet. Subsequent insulation of the electrode with parylene results in a hybrid electrode for SECM-SICM measurements. Electrode fabrication is straightforward and highly parallel. For image collection, ionic current measured at the nanopipet both controls the position of the electrode with respect to the membrane surface and reports the local conductance in the vicinity of the nanopipet, while faradaic current measured at the Au electrode reports the presence of redox-active molecules. Application of a transmembrane potential difference affords additional control over migration of charged species across the membrane.     

Interfacial bridge-mediated electron transfer: mechanistic analysis based on electrochemical kinetics and theoretical modelling

Understanding the physical and chemical factors that control the kinetics of interfacial electron-transfer (ET) reactions is important for a large number of technological applications. The present article describes electrochemical kinetic studies of these factors, in which standard interfacial ET rate constants (k(0)(l)) have been measured for ET between substrate Au electrodes and various redox couples attached to the electrode surfaces by variable lengths (l) of oligomethylene (OM), oligophenylenevinylene (OPV) and oligophenyleneethynylene (OPE) bridges, which were constituents of mixed self-assembled monolayers (SAMs). The k(0)(l) measurements employed the indirect laser-induced temperature jump (ILIT) technique, which permits the measurement of interfacial ET rates that are orders of magnitude faster than those measurable by conventional techniques using the macroelectrodes that are the most convenient substrates for the mixed SAMs. The robustness of the measured rate constants (k(0)(l)), together with the Arrhenius activation energies (E(a)(l)) and preexponential factors (A(l)), is demonstrated by their invariance with respect to several experimental system parameters (including the chemical nature and length of the diluent component of the mixed SAM). Analysis of the kinetic results demonstrates that all of the observed interfacial ET processes proceed through a common type of transition state (predominantly associated with solvent reorganization around the redox moiety) and that the actual ET step involves direct electronic tunnelling between the Au electrode and the redox moiety. However, for the full range of l investigated, a global exponential decay of A(l) is not found for any of the three types of bridges. Possible reasons for this behavior, including the role of rate determining steps associated with adiabatic mechanisms within or beyond the transition state theory framework, are discussed, and comparisons with related conductance measurements are presented.     

SECM study of solute partitioning and electron transfer at the ionic liquid/water interface

Molecular partitioning and electron-transfer kinetics have been studied at the ionic liquid/water (IL/water) interface by scanning electrochemical microscopy (SECM). The ionic liquid C8mimC1C1N is immiscible with water and forms a nonpolarizable interface when in contact with it. Partitioning of ferrocene (Fc) across the IL/water interface was studied by SECM and found to be kinetically fast with a partition coefficient CIL/CW of 2400:1. The partition coefficient value was measured by SECM under quasi-steady-state conditions without waiting for complete solute equilibration. To investigate the kinetics of the electron transfer (ET) between aqueous ferricyanide and Fc dissolved in IL, a new approach to the analysis of the SECM current-distance curves was developed to separate the contributions of Fc partitioning and the ET reaction to the tip current. Several combinations of different aqueous and nonaqueous redox species were investigated; however, only the Fc/Fe(CN)63- system behaved according to the Butler-Volmer formalism over the entire accessible potential range.     

Theoretical study of electron, proton, and proton-coupled electron transfer in iron bi-imidazoline complexes.

A comparative theoretical investigation of single electron transfer (ET), single proton transfer (PT), and proton-coupled electron transfer (PCET) reactions in iron bi-imidazoline complexes is presented. These calculations are motivated by experimental studies showing that the rates of ET and PCET are similar and are both slower than the rate of PT for these systems (Roth, J. P.; Lovel, S.; Mayer, J. M. J. Am. Chem. Soc. 2000, 122, 5486). The theoretical calculations are based on a multistate continuum theory, in which the solute is described by a multistate valence bond model, the transferring hydrogen nucleus is treated quantum mechanically, and the solvent is represented as a dielectric continuum. For electronically nonadiabatic electron transfer, the rate expressions for ET and PCET depend on the inner-sphere (solute) and outer-sphere (solvent) reorganization energies and on the electronic coupling, which is averaged over the reactant and product proton vibrational wave functions for PCET. The small overlap of the proton vibrational wave functions localized on opposite sides of the proton transfer interface decreases the coupling for PCET relative to ET. The theory accurately reproduces the experimentally measured rates and deuterium kinetic isotope effects for ET and PCET. The calculations indicate that the similarity of the rates for ET and PCET is due mainly to the compensation of the smaller outer-sphere solvent reorganization energy for PCET by the larger coupling for ET. The moderate kinetic isotope effect for PCET arises from the relatively short proton transfer distance. The PT reaction is found to be dominated by solute reorganization (with very small solvent reorganization energy) and to be electronically adiabatic, leading to a fundamentally different mechanism that accounts for the faster rate.     

Electron-transfer studies in a lyotropic columnar hexagonal liquid crystalline medium

We have studied the electron-transfer properties of some redox systems on a gold electrode in a lyotropic hexagonal columnar liquid crystalline phase (H1 phase) using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The liquid crystalline medium consists of the nonionic surfactant Triton X-100 and water. The redox reactions that have been studied are ferrocene/ferricenium, [Fe(CN)6]3-/4-, and [Ru(NH3)6]3+/2+. We have confirmed by polarizing optical microscopy that the liquid crystalline nature of the medium is maintained even after the addition of the redox species and the supporting electrolyte. The CV studies show a significant shift in the half-peak potentials of these redox reactions in the liquid crystalline medium. From the EIS studies, we have measured the diffusion coefficients and the kinetic parameters for the redox species. These results are discussed and compared with the values obtained in the conventional solvent medium. The CV and impedance studies demonstrate that the hexagonal columnar phase provides a novel controlled environment for the study of electron-transfer reactions in biological and physiological media.     

Coupled zinc transport through a bis(2-ethylhexyl)phosphoric acid solid-supported liquid membrane from aqueous perchlorate media

The rate of Zn(II) transport from 1.0 M (Na,H)ClO₄ aqueous media through a liquid membrane consisting of bis(2-ethylhexyl)phosphoric acid (HDEHP, HR) dissolved in Isopar-H and a teflon-type solid support, has been investigated as a function of the chemical composition of the system and the hydrodynamic conditions at 25°C. The measured transfer rates have been explained in terms of aqueous diffusion, diffusion of ZnR₂(HR)₂ and ZnR₂(HR) species through the liquid membrane and the rate of chemical reactions of Zn(II) in this system. The results are in agreement with the kinetic and equilibrium models proposed for this sytem in previous studies.     

Tuning the rate and pH accessibility of a conformational electron transfer gate

Methods to fine-tune the rate of a fast conformational electron transfer (ET) gate involving a His-heme alkaline conformer of iso-1-cytochrome c (iso-1-Cytc) and to adjust the pH accessibility of a slow ET gate involving a Lys-heme alkaline conformer are described. Fine-tuning the fast ET gate employs a strategy of making surface mutations in a substructure unfolded in the alkaline conformer. To make the slow ET gate accessible at neutral pH, the strategy involves mutations at buried sequence positions which are expected to more strongly perturb the stability of native versus alkaline iso-1-Cytc. To fine-tune the rate of the fast His 73-heme ET gate, we mutate the surface-exposed Lys 79 to Ala (A79H73 variant). This mutation also simplifies ET gating by removing Lys 79, which can serve as a ligand in the alkaline conformer of iso-1-Cytc. To adjust the pH accessibility of the slow Lys 73-heme ET gate, we convert the buried side chain Asn 52 to Gly and also mutate Lys 79 to Ala to simplify ET gating (A79G52 variant). ET kinetics is studied as a function of pH using hexaammineruthenium(II) chloride (a6Ru2+) to reduce the variants. Both variants show fast direct ET reactions dependent on [a6Ru2+] and slower gated ET reactions that are independent of [a6Ru2+]. The observed gated ET rates correlate well with rates for the alkaline-to-native state conformational change measured independently. Together with the previously reported H73 variant (Baddam, S.; Bowler, B. E. J. Am. Chem. Soc. 2005, 127, 9702-9703), the A79H73 variant allows His 73-heme-mediated ET gating to be fine-tuned from 75 to 200 ms. The slower Lys 73-heme (15-20 s time scale) ET gate for the A79G52 variant is now accessible over the pH range 6-8.     

Photoinduced intramolecular electron-transfer reactions of reconstituted met- and zinc-myoglobins appending acridine and methylacridinium ion as DNA-binders

Three types of reconstituted met- and zinc-myoglobin (metMb and ZnMb) dyads, ZnMbAc(4)Me+, ZnMbAc(6)Me+, and metMbAc(6) have been prepared by incorporating chemically modified metalloporphyrin cofactor appending an acridine (Ac) or a methylacridinium ion ([AcMe]+) into apo-Mb. In the bimolecular system between ZnMb and [AcMe]+, the photoexcited triplet state of ZnMb, 3(ZnMb)*, was successfully quenched by [AcMe]+ to form the radical pair of ZnMb cation (ZnMb*+) and reduced methylacridine ([AcMe]*), followed by a thermal back ET reaction. The rate constants for the intermolecular quenching ET (kq) and the back ET reaction (kb) at 25 degrees C were successfully obtained as kq = (8.8 +/- 0.4) x 10(7) M(-1) s(-1) and kb = (1.2 +/- 0.1) x 10(8) M(-1) s(-1), respectively. On the other hand, in case of the intramolecular photoinduced ET reactions of ZnMbAc(4)Me+ and ZnMbAc(6)Me+ dyads, the first-order quenching rate constants (kET) of 3(ZnMb)* by [AcMe]+ moiety were determined to be kET = 2.6 x 10(3) and 2.5 x 10(3) s(-1), respectively. When such ET occurs along the alkyl spacer via through-bond mechanism at the surface of Mb, the obtained kET is reasonable to provide decay constant of beta (1.0-1.3 A(-1)). Upon photoirradiation of [AcMe]+ moiety, kinetic studies also presented the intramolecular quenching reactions from the excited singlet state, 1([AcMe]+)*, whose likely process is the photoinduced energy-transfer reaction. For metMbAc(6) dyad, steady-state fluorescence was almost quenched, while the signal around 440 nm gradually appeared in the presence of various concentrations of DNA. Our study implies that synthetic manipulation at the Mb surface, by using an artificial DNA-binder coupled with photoinduced reaction, may provide valuable information to construct new Mb-DNA complex and sensitive fluorescent for DNA.     

Stability of supported liquid membranes containing Acorga P-50 as carrier

The coupled transport of copper(II) ions through supported liquid membranes (SLM) was examined in zeroth order steadystate kinetic regime using Acorga P-50 as carrier. SLM life-times were estimated using a new method based on kinetic analysis. The influence of different experimental conditions on the transport rate allowed to establish various factors determining membrane stability. SLM life-time seems to depend in a clearcut way on both the type of polymeric support and the nature of liquid membranes suggesting that solute-solvent (and polymer solvent) interactions play a dominant role in membrane stability. It was shown that water transport, if any, occurs only through empty pores of the polymeric support. No clear effect of osmotic pressure gradient on liquid membrane stability was found.