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Electrochemistry
in Ionic Liquids
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Introduction
Ionic liquids are an exciting environment for electrochemical investigations. Although ionic liquids have been known since 1914,1-4 their initial use for electrochemical analysis of redox species was slow, taking over half a century for the use of a chloroaluminate ionic liquid to investigate a metal redox centre to be reported.5 Even after this investigation was published, studies on the use of ionic liquids as electrolytes were minimal, although by the 1980s and 1990s, the tide was turning and the first generation of ionic liquids, haloaluminates, were becoming active areas of electrochemical research.6 Although ionic liquids had become more prominent, their ease of use in ambient conditions was very limited, hindering their overall applicability. This changed in 1992, when the first of the second generation of ionic liquids was reported.7 The second generation started with the investigation of 1- ethyl-3-methylimidazolium (EMIM+) ionic liquids. Unlike the prior generation, the
anion was specifically chosen to form an inert ionic liquid which was easily handled under ambient conditions. By combining the EMIM+ cation with NO
3-, NO2-, BF4-,
MeCO2-, or SO4- the resulting ionic liquid could be synthesized without any special
care aside from drying under vacuum at elevated temperatures.7 The introduction of an easily handled second generation of ionic liquids opened the door for the explosion of work on electrochemistry in ionic liquids in the 2000s.3 Ionic liquids are now used in electrochemical investigations because of their wide potential window, high thermal stability, low volatility, high conductivity, and the limitless variety of ionic liquids available by changing the combination of anion and cation.
Redox active monolayers are important in molecular electronics measurements for several reasons. 1) In-depth analysis of the electrochemistry of redox active monolayers is often the first step in assessing a molecule for further analysis by
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molecule conductance studies. 2) The interpretation of the electrochemistry of monolayers can allow for determination of electron transfer between the substrate and redox centre and assessment of the linking groups. 3) Redox active monolayers may themselves be important in the formation of hybrid molecular electronics systems.
When looking at redox active molecular wires, investigation of the electrochemical activity of the adsorbed species is often the first step in assessing the molecules’ potential as a molecular wire. This has been the case for many redox active molecules including, although not limited to, viologen wires,8-12 pTTF containing wires,10, 13 and redox active Ru wires.14, 15 By assessing the electrochemistry of a redox active molecule adsorbed on the electrode, electron transfer to and from that molecule can be assessed which has eventual implications on the conductance behaviour of the molecule. This is particularly true when the conductance is investigated as a function of the electrochemical potential. At a more simplistic level, the initial assessment of the electrochemistry of an adsorbed redox species is necessary to ensure the redox chemistry is stable in the electrochemical potential measurement window.
The investigation of the interaction of an electrode surface with a bound redox molecule is insightful in itself for studies of relevance to molecular electronics. These sorts of studies are important in determining not only the rate of electron transfer,16, 17 but also the mechanism of electron transfer,18 whilst also allowing the effect of changing the molecular wire on electron transfer, to be determined.17, 19 By investigating the electron transfer between a bound redox species and the electrode, the electron transfer through a saturated alkane molecular bridge has been seen to give rise to an attenuation factor of ~1.0 Å.16, 17 The same technique of measuring electron transfer from electrode to redox active group shows more favourable electron transfer through OPV and OPE molecules with noticeably lower β-values.17, 19 The capabilities
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of using redox active monolayers to investigate electron transfer for future exploitation in molecular electronics were demonstrated in 2011, when electron transport through a monolayer of a 120 Å 80mer helical peptide bound to Au by a disulphide, and terminated in a ferrocene group was measured.20 This work showed long-range charge transfer through the peptide to the ferrocene to produce a voltammetric response, and allowed the rate of charge transfer and the charge transport mechanism to be determined. Through this work charge transfer through the self-assembled monolayer of peptide was determined to occur by a hopping mechanism in which a hole is transferred from amide to amide, forming and removing radical amide cations until the ferrocene is oxidised. This study demonstrated that redox active monolayers have facilitated charge transfer to be measured through very long helical peptides, which are one of the longest molecular electron transfer systems investigated. While redox active monolayers hold great potential for investigating molecular electronics, they also hold great potential for the use in final devices in molecular electronics.
Self-assembled monolayers have been envisaged as potential components in futuristic molecular electronics devices, although technological implementation still seems a long way off. More fundamental studies have been performed with this envisaged aim by investigating the ability of various redox active monolayers in memory devices.21-23 Measurements of hybrid molecular devices, i.e. those composed of molecular monolayers on Si, are being made to assess their potential as computational memory. The investigation of a Co-porphyrin for a Flash memory gate structure showed improvements over similar porphyrin free structures with better memory retention, and negligible memory loss.22 DRAM, a non-volatile memory requiring power for storage, has also shown improvements when molecular monolayers are used.21 Self-assembled monolayers terminated in ferrocene have been
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proposed as a good molecular alternative for DRAM devices. It has been contended that ferrocene terminated monolayers may allow lower power consumption, as this is related to the potential needed to oxidise ferrocene, while having higher charge density on a unit area basis because of the small size of the ferrocene.21 These investigations were aimed at a first level demonstration that self-assembled monolayers can be competitive in computational memory.
The electrochemistry of redox active self-assembled monolayers has been investigated as the first stage for molecular electronics studies of redox active molecular wires. These studies have assessed electron transfer to/from the electrode to the tethered redox moiety, as assisted by a molecular wire, in a straightforward manner. Ionic liquids have allowed for investigations on the redox active monolayers which are not otherwise possible, particularly in aqueous electrolytes. With use of room temperature ionic liquids, the redox properties of a viologen containing molecular wire, through both electron transfer processes have been investigated. Furthermore, the use of ionic liquids have allowed the rate of electron transfer through covalent and hydrogen bonded ferrocene to be assessed, with the effect of electrolyte environment seen.
Aim
The second generation of ionic liquids is an interesting area of research for electrochemistry. The unique characteristics afforded by using an ionic liquid rather than an aqueous or organic electrolyte can be exploited for investigations in molecular electronics, particularly with redox active molecules. By utilizing ionic liquids, this work aims to study the electrochemistry of redox active monolayers on Au. In this chapter it will be demonstrated that ionic liquids allow the investigation of multiple
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redox states of molecules, as well as monolayers functionalized with redox active molecules by exploitation of hydrogen bonding. The electrochemistry of various redox systems in ionic liquids will be compared with their aqueous electrochemistry.
Methods
Cyclic voltammetry was performed on an Autolab PGSTAT30 computer controlled instrument running GPES. Analysis of resulting voltammograms was performed in GPES, and/or Origin 8.9, depending on limitations of the former. All CVs were performed between at least 0.05 Vs-1 and 1.0 Vs-1.
For aqueous investigations, a three electrode setup with an Au(111) bead WE, Pt mesh CE, and SCE RE was used. Both the CE and WE were prepared through annealing in a Bunsen flame. All 3 electrodes were in separate compartments of a 50 ml cell, with the reference electrode separated by a Luggin capillary, and the WE contacted the electrolyte with a hanging meniscus. Aqueous electrochemistry was performed after at least 20 minutes bubbling with oxygen free nitrogen. Aqueous electrolytes were prepared using Milli-Q® water (18 MΩ)
Ionic liquid based studies were performed with a three electrode setup composed of a Au(111) bead, and Pt wire CE and QRE. The WE was placed so as to achieve a stable hanging meniscus. It should be noted the ionic liquid Fc experiments were performed using an ArrandeeTM slide sealed at the bottom of the electrochemical cell. All cells used were > 1.5 ml in capacity, prepared in a nitrogen atmosphere glovebox, and sealed prior to removal. All potentials are quoted against a Fc/Fc+ internal reference, after all necessary measurements were performed. To dissolve Fc in the ionic liquids, gentle heating was necessary. Ionic liquids were prepared by vacuum drying for at least 18 hours at 120 °C, with stirring.
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Ferrocene
The electrochemistry of ferrocene was measured as a 2.5 mM solution in BMIM-TFSA and BMIM-PF6, and a 5 mM solution in BMIM-OTf. Fc was dissolved
by gentle heating of the ionic liquid. Analogous aqueous electrochemistry was performed on 2.5 mM FcCOOH in 0.2 M sodium phosphate buffer.
Viologen Compounds
The aqueous electrochemistry of paraquat was studied using a 1 mM paraquat/0.3 M KCl solution, made from Milli-Q® water. A three electrode, three compartment cell was employed, in which a Luggin capillary connected the reference and working electrode compartments. The working electrode was a Au(111) bead, with a hanging meniscus, a Pt mesh counter electrode, and the reference electrode was SCE. Before carrying out measurements, the system was bubbled with oxygen free nitrogen for 20 minutes, and kept under nitrogen throughout the duration of the experiment.
The electrochemistry of the viologen compounds in ionic liquid were all performed in the same manner. All compounds were measured as 7.5 mM in BMIM- OTf solutions. On their own, these compounds are sparingly soluble in BMIM-OTf, therefore, to form a solution, they were dissolved in the smallest amount of methanol possible and to this 1 ml of BMIM-OTf was added. As the addition of any solvent to BMIM-OTf can reduce the potential window, the methanol was heated off by the ‘sweeping method.’24 To do this, the solution was heated, in the glovebox, at about
100 °C with nitrogen bubbled directly into the solution, for 1 hour.
Monolayers of 6V6 were formed on the surfaces of a Au(111) bead electrode and investigated in aqueous and ionic liquid electrolytes. To successfully form
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monolayers of 6V6 the thioacetate protecting group was removed to reveal the free thiol. To deprotect the 6V6 a 1:1 1 mM solution of 6V6 and KOH in methanol was made and left for 2 hours, after which point a colour change in the solution had occurred. The Au(111) bead was prepared by annealing in a Bunsen flame and immersed in the solution, after cooling, for 1.5 hours. Upon removal the electrode was rinsed with ethanol and Milli-Q® water and dried with nitrogen. Aqueous electrochemistry was performed in 0.1 M Na2SO4. Ionic liquid electrochemistry was
performed in vacuum dried BMIM-OTf.
Laviron Analysis for Ferrocene Terminated Monolayers
The electrochemistry of a series of Fc terminated monolayers on a Au(111) bead electrode was investigated in aqueous 0.1 M HClO4 and BMIM-OTf. The
monolayers fall into two categories, covalently bonded Fc, and hydrogen bonded Fc. The covalently bonded Fc monolayers are FcC11SH, FcC6SH, and FcCOOH, the
hydrogen bonded Fc monolayers are 6-mercaptohexanoic acid, 8-mercaptooctanoic acid, and 11-mercaptoundecanoic acid monolayers with FcCOOH hydrogen bonded to the carboxylic acid end group. The ferrocenyl alkanethiol monolayers were formed by 1 hour adsorption in a mixed adsorption solution of 1 mM: 3 mM ferrocenyl alkanethiol: alkanethiol in ethanol, where the alkanethiol has one less CH2 unit. A 0.25
mM FcCOOH in DCM solution was used to form the FcCOOH monolayer with 45 minutes adsorption. To form the hydrogen bonded series, the carboxylic acid terminated thiol monolayer was first formed from 1 hour adsorption in a 10 mM in methanol solution. The electrode was then rinsed with ethanol and water and transferred to the FcCOOH in DCM solution for 45 minutes. All monolayers were rinsed with ethanol and Milli-Q® water after removal from the adsorption solution
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used. All systems were investigated in the ionic liquid BMIM-OTf, only the FcC11SH/10-decanethiol monolayer was investigated in the aqueous electrolyte.
Methods of Analysis
Randles-Ševčik AnalysisThe Randles-Ševčik equation is extensively used in electrochemistry to determine the diffusion coefficient of a dissolved system. The diffusion coefficient is related to the scan rate by:25-28
|𝐼𝑝| = 0.4463 (𝐹3
𝑅𝑇) 1/2
𝐴𝑐∗𝐷1/2𝑣1/2 (Eq. 1)
Where Ip is the peak current, F Faraday’s constant, R the gas constant, T the absolute temperature, A the area of the electrode, c* the bulk concentration, D the diffusion coefficient and v the scan rate. This equation shows a linear relation between Ip and
v1/2. As a result of this relationship, by plotting Ip as a function of v1/2 the diffusion coefficient of the system can be found from the slope of this plot. The Randles-Ševčik equation allows for the diffusion coefficient to be easily determined from cyclic voltammetry using a range of scan rates.
Nicholson Analysis
The Nicholson analysis allows for the determination of the rate constant of electron transfer for a quasi-reversible system. This analysis allows cyclic voltammetry to be used to accurately measure the rate constant of electron transfer, with the assumption that only the soluble oxidised and reduced species are formed as a result of charge transfer.29 The Nicholson analysis relates k0 to ΔEp through the use of a standard working curve.29-31 The working curve directly links the charge transfer parameter, Ψ, to ΔEp, allowing Ψ to be read from the curve when ΔEp is known.29-32 If
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the diffusion coefficients are known, once Ψ is determined the rate constant of electron transfer can be found. Ψ is related to k by the following equation:29, 33
𝛹 = 𝛾𝛼𝑘 (𝜋𝑎𝐷𝑂) 1 2 (Eq. 2) Where𝛾 = (𝐷𝑂
𝐷𝑅), α is the transfer coefficient, 𝑎 = 𝑛𝐹𝑣/𝑅𝑇, and DO and DRare the
diffusion coefficients of the oxidised and reduced species. For this analysis to be successful ΔEp values linked to intermediate values of Ψ should be used.29 Also α must be between 0.3 and 0.7, as in this range peak separation is only dependent on Ψ.32 In most cases, however, the effect of α is small and therefore is assumed to be 0.5.33 Finally, the success of this analysis is dependent on there being minimal iR drop.29, 32 If these assumptions hold true then the Nicholson analysis is a powerful technique for the determination of the rate constant of electron transfer from cyclic voltammetry.
Laviron Analysis
Utilizing the Laviron analysis, the rate constant of electron transfer between an adsorbed redox species and the substrate can be easily determined using cyclic voltammetry.34 The Laviron analysis works by relating the peak separation of a system
over a range of scan rates. The aim of the range of scan rates is to probe both the fully reversible and fully irreversible domains. In the fully reversible domain there is little change in peak separation as scan rate increases, whereas in the fully irreversible domain small changes in scan rate result in large changes in peak separation.35 By plotting peak separation of the system as a function of v1/2 the two domains become
readily apparent in the form of a trumpet plot. To determine k a straight line is fitted to both domains in the trumpet plot, and the scan rate at which these intercept is noted. Using the intercept scan rate, k can be found from the following relationship:35
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(𝛼𝑛𝐹𝑣
𝑅𝑇𝑘𝑠) = 1 (Eq. 3)
It should be noted though, that a number of assumptions are made when using this treatment. The assumptions made include: 1) The oxidized and reduced species are strongly adsorbed with minimal desorption.34, 36 2) Only the adsorbed species are involved in the measured electrochemistry.34, 36 3) All adsorption sites are equal, with the oxidized and reduced species having the same surface area occupancy.36 4) All adsorbed redox active species take part in the electron transfer reaction.36 5) The
adsorbed redox centres do not interact with one another.36, 37 By making these assumptions the Laviron analysis allows a straightforward determination of the rate constant of electron transfer between the electrode and an adsorbed species.
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Results and Discussion
Ferrocene Solution Electrochemistry
-0.30 -0.15 0.00 0.15 0.30 -4.0x10-4 -2.0x10-4 0.0 2.0x10-4 4.0x10-4 I/ A cm -2 E/V vs Fc/Fc+ -0.4 -0.2 0.0 0.2 0.4 0.6 -2.0x10-4 -1.0x10-4 0.0 1.0x10-4 2.0x10-4 I/A cm -2 E/V vs Fc/Fc+ -0.2 0.0 0.2 0.4 -2.0x10-4 -1.0x10-4 0.0 1.0x10-4 2.0x10-4 I/ A cm -2 E/V vs Fc/Fc+ -0.15 0.00 0.15 0.30 -1.50x10-3 -7.50x10-4 0.00 7.50x10-4 1.50x10-3 I/ A cm -2 E/V vs SCE (a) (b) (c) (d)
Figure 1: The electrochemistry of Fc in (a) BMIM-OTf, (b) BMIM-PF6, and (c)
BMIM-TFSA. (d) The electrochemistry of FcCOOH in 0.2 M sodium phosphate
buffer. All ionic liquid electrochemistry is performed at a Au(111) ArrandeeTM slide
WE, against Pt wire CE and QRE. The result was referenced to Fc/Fc+. Aqueous
electrochemistry was performed at a Au(111) bead electrode, with a Pt CE, and
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Table 1: Diffusion coefficients and rate constants of electron transfer for Fc systems.
System Da / cm 2 s-1 Dc / cm 2 s-1 k / cm s-1 5 mM Fc in BMIM-OTf 2.27 x 10 -8 3.63 x 10-8 1.95 x 10-4 2.5 mM Fc in BMIM-TFSA 3.06 x 10 -8 4.97 x 10-8 4.38 x 10-4 2.5 mM Fc in BMIM-PF6 8.82 x 10 -9 1.50 x 10-8 1.20 x 10-4 2.5 mM FcCOOH in 0.2 M Sodium Phosphate Buffer 3.40 x 10-6 3.52 x 10-6 2.26 x 10-2
To gain a better understanding of electrochemistry in ionic liquids, ferrocene was investigated in BMIM-OTf, BMIM-TFSA, and BMIM-PF6. For comparison
aqueous investigations were performed on ferrocene carboxylic acid, because ferrocene is not soluble in aqueous electrolytes. Based on the literature, the solubility of ferrocene in ionic liquids is questionable,38 however, with just some gentle heating relatively high concentration ferrocene solutions could be made. The electrochemistry of all four solutions against Au(111) is shown in Figure 1. These voltammograms show a degree of sloping, dependent on the ionic liquid. This sloping likely arises from residual water content. As different ionic liquids have different hydrophobicities it is unsurprising that the sloping changes with ionic liquid. The large range of scan rates