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The use of additives to modulate metal electrodeposition from deep eutectic solvents has, to date, apparently been of little interest given the dearth of such studies in the literature. Here, we have actively investigated the effects of nicotinic acid (NA) on the electrodeposition of copper in a choline chloride (ChCl)-ethylene glycol (EG)-based deep eutectic solvent (DES), (1ChCl:2EG), considered a “green solvent” due to its physiochemical properties. Bright copper deposits were formed when NA was added to the Cu electrolyte, while a dull Cu deposit was produced in its absence. New Cu species were found to have formed in the 1ChCl:2EG-based liquid when NA was added to the electrolyte. A number of analytical techniques, in this instance cyclic voltammetry, chronoamperometry, and chronocoulometery, have been employed to determine the various electrochemical properties, nucleation mechanisms, and kinetics of the Cu species reported herein. The diffusion coefficient for the Ethaline-Cu system was found to be affected by the concentration of NA. An electrochemical quartz crystal microbalance (EQCM) was used to monitor the current efficiency of the copper deposition in both systems. The morphologies, thicknesses, roughnesses, and crystal structures of the copper electrodeposited from the NA-modified electrolyte were characterised via scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD), which between them demonstrate that the NA introduced into this system acts as a highly effective brightener, producing highly uniform and smooth copper deposits.

Ionic liquids (ILs) and deep eutectic solvents have been used for the extraction of molecules, particularly natural products. An often studied system is that for thiophene removal from oil. In the current study, ILs have been used for the removal of thiophene (Th), benzothiophene (BT), and dibenzothiophene by liquid–liquid extraction. The equilibrium can be shifted by polymerizing the thiophenic compounds both electrochemically and chemically. A 1:1 mixture of 1-butyl-3-methylimidazolium chloride (Bmim)Cl and FeCl3 was used to extract Th and BT from alkane layers using electropolymerization to shift the position of the equilibrium. While the process could be carried out, the kinetics of polymer formation were too slow to make this a viable process. The final part of the study used a 1:2 (Bmim)Cl/FeCl3 mixture to chemically remove sulfur-containing compounds from alkane layer. It was shown that the chemical polymerization reaction of Th is around 1500 times faster than electrochemical polymerization. Issue...

Despite the importance of ionic liquids in a variety of fields, little is understood about the behaviour of protons in these media. The main difficulty arises due to the unknown activity of protons in non-aqueous solvents. This study presents acid dissociation constants for nine organic acids in deep eutectic solvents (DESs) using standard pH indicator solutes. The pKIn value for bromophenol blue was found by titrating the DES with triflic acid. The experimental method was developed to understand the acid-base properties of deep eutectic solvents, and through this study it was found that the organic acids studied were slightly less dissociated in the DES than in water with pKa values between 0.2 and 0.5 higher. pKIn values were also determined for two ionic liquids, [Bmim][BF4] and [Emim][acetate]. The anion of the ionic liquid changes the pH of the solution by acting as a buffer. [Emim][acetate] was found to be more basic than water. It is also shown that water significantly affects the pH of ionic liquids. This is thought to arise because aqueous mixtures with ionic liquids form heterogeneous solutions and the proton partitions into the aqueous phase. This study also attempted to develop an electrochemical pH sensor. It was shown that a linear response of cell potential vs. ln aH+ could be obtained but the slope for the correlation was less than that obtained in aqueous solutions. Finally it was shown that the liquid junction potential between two reference electrodes immersed in different DESs was dependent upon the pH difference between the liquids.

Deep eutectic solvents (DESs) are mixtures of quaternary ammonium halides with hydrogen bond donors and are increasingly being used in applications where they are in contact with metals. This study investigates the corrosion of iron, nickel and aluminium in DESs. It shows that none of the metals show significant corrosion when glycerol is used as a hydrogen bond donor but when an acidic hydrogen bond donor such as oxalic acid is used, both iron and aluminium show catastrophic corrosion as may be expected. Surprisingly, however, nickel does not corrode in the acidic DES, Oxaline. The differences in corrosion observed for aluminium and iron are explained in terms of passivating films and the slowness of the oxygen reduction reaction despite the relatively high gas solubility. The high chloride ion content (roughly 4 mol dm−3) has a relatively small effect on the corrosion of the three metals. The formation of a passive layer as a result of hydrogen bond donor-metal ion complexes is shown to be more important. It is proposed that the low corrosion rates of some metals resulted from the slow rate of the cathodic reaction resulting from the high viscosity, low activity of water and low proton mobility.

It is reported in this study that the deep eutectic solvent (DES), (Ethylene glycol)2(Choline chloride), (2Eg:ChCl) is an effective medium in the electrolytic removal of the Fe-rich layer from Ni-based hot isostatic press (HIP) consolidation and that it is capable of sustaining etching at higher rates and at higher current efficiencies than a comparable aqueous electrolyte formulated from methane sulphonic acid/glycolic acid (MSA/GA). At high etch rates, the surface finish is not as good using 2Eg:ChCl, but high etch rates, current efficiency and excellent surface finish can be obtained from a 90%/10% hybrid mixture of 2Eg:ChCl MSA/GA electrolytes. This study has set out to compare the electropolishing and bulk electrolytic etching of HIP-formed bodies fabricated from RR1000 Ni-based superalloys in aqueous methane sulphonic acid/glycolic acid (MSA/GA) electrolyte and in DES-type ionic liquids. It is shown that the HIP alloy can be effectively removed under mild conditions using DES electrolytes that are o...

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.

The anodic dissolution of metals is an important topic for battery design, material finishing and metal digestion. Ionic liquids are being used in all of these areas but the research on the anodic dissolution is relatively few in these media. This study investigates the behaviour of 9 metals in an ionic liquid [C 4 mim][Cl] and a deep eutectic solvent, Ethaline, which is a 1:2 mol ratio mixture of choline chloride and ethylene glycol. It is shown that for the majority of metals studied a quasi-passivation of the metal surface occurs, primarily due to the formation of insoluble films on the electrode surface. The behaviour of most metals is different in [C 4 mim][Cl] to that in Ethaline due in part to the differences in viscosity. The formation of passivating salt films can be decreased with stirring or by increasing the electrolyte temperature, thereby increasing ligand transport to the electrode surface.

Metal electrodeposition using ionic liquid electrolytes and deep eutectic solvents is now well known but to our knowledge for electrolytic deposition of metals such as nickel no direct comparison has thus far been drawn between deposition using aqueous solutions and DES under otherwise identical conditions. In the current study it is shown that nickel deposition can be carried out with similar deposition rates in aqueous and ionic media despite the significant differences in viscosity and conductivity. It is, however, shown that in ionic media the morphology of the deposits is markedly different from that achieved using a Watts nickel bath and that one aspect of these differences manifests itself in significant increase in the coating hardness. It is proposed that the observed morphology differences occur due to the variations of nickel speciation in each electrolyte environment.

In this study we compare the electrochemical and structural properties of three gold salts AuCl, AuCN and KAu(CN)2 in a Deep Eutectic Solvent (DES) electrolyte (Ethaline 200) in order to elucidate factors affecting the galvanic deposition of gold coatings on nickel substrates. A chemically reversible diffusion limited response was observed for AuCl, whereas AuCN and KAu(CN)2 showed much more complicated, kinetically limited responses. Galvanic exchange reactions were performed on nickel substrates from DES solutions of the three gold salts; the AuCN gave a bright gold coating, the KAu(CN)2 solution give a visibly thin coating, whilst the coating from AuCl was dull, friable and poorly adhesive. This behaviour was rationalised by the differing speciation for each of these compounds, as evidenced by EXAFS methods. Analysis of EXAFS data shows that AuCl forms the chlorido-complex [AuCl2](-), AuCN forms a mixed [AuCl(CN)](-) species, whereas KAu(CN)2 maintains its [Au(CN)2](-) structure. The more labile Cl(-) enables easier reduction of Au when compared to the tightly bound cyanide species, hence leading to slower kinetics of deposition and differing electrochemical behaviour. We conclude that metal speciation in DESs is a function of the initial metal salt and that this has a strong influence on the mechanism and rate of growth, as well as on the morphology of the metal deposit obtained. In addition, these coatings are also extremely promising from a technological perspective as Electroless Nickel Immersion Gold (ENIG) finishes in the printed circuit board (PCB) industry, where the elimination of acid in gold plating formulation could potentially lead to more reliable coatings. Consequently, these results are both significant and timely.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

The speciation of metals in solution controls their reactivity, and this is extremely pertinent in the area of metal salts dissolved in ionic liquids. In the current study, the speciation of 25 metal salts is investigated in four deep eutectic solvents (DESs) and five imidazolium-based ionic liquids using extended X-ray absorption fine structure. It is shown that in diol-based DESs M(I) ions form [MCl2](-) and [MCl3](2-) complexes, while all M(II) ions form [MCl4](2-) complexes, with the exception of Ni(II), which exhibits a very unusual coordination by glycol molecules. This was also found in the X-ray crystal structure of the compound [Ni(phen)2(eg)]Cl2·2eg (eg = ethylene glycol). In a urea-based DES, either pure chloro or chloro-oxo coordination is observed. In [C6mim][Cl] pure chloro complexation is also observed, but coordination numbers are smaller (typically 3), which can be explained by the long alkyl chain of the cation. In [C2mim][SCN] metal ions are entirely coordinated by thiocyanate, either through the N or the S atom, depending on the hardness of the metal ion according to the hard-soft acid-base principle. With weaker coordinating anions, mixed coordination between solvent and solute anions is observed. The effect of hydrate or added water on speciation is insignificant for the diol-based DESs and small in other liquids with intermediate or strong ligands. One of the main findings of this study is that, with respect to metal speciation, there is no fundamental difference between deep eutectic solvents and classic ionic liquids.

A non-aqueous zinc–polyaniline secondary battery was fabricated with polyaniline Emeraldine base as cathode and zinc metal as anode in an electrolyte consisting of 0.3 M zinc-bis(trifluoromethyl-sulfonyl)imide Zn(TFSI) 2 dissolved in propylene carbonate. We observed that the formation of the battery required a prerequisite condition to stabilize the interfaces in order to maintain a stable capacity. The battery suffered from Zn dissolution which induces a competition between concurrent Zn dissolution and plating when the battery is in charge mode, and thus inefficient cycles are obtained. The capacity and coulombic efficiency of the battery depends on the charge–discharge rates. We propose cycling protocols at different rates to determine the steady-state rates of competing reactions. When the cell is cycled at ≥1 C rate, the coulombic efficiency improves. The maximum capacity and energy densities of the battery are 148 mAhg −1 and 127 mWhg −1 , respectively for discharge at C/2. The battery was successively charged/discharged at constant current densities (1C rate), and high cycling stability was obtained for more than 1700 cycles at 99.8% efficiency. Zinc dissolution and self discharge of the battery were investigated after 24 h of standby. The investigation showed that the battery experiences a severe self-discharge of 48% per day.

Although mineral oils are commonly used as lubricants their emission particularly in marine environments can cause significant impact. In the current study the properties of water miscible deep eutectic solvents and ionic liquids are compared with a typical mineral base oil to ascertain their efficacy for potential marine lubricants. The environmental compatibility of some of the liquids, particularly choline chloride and glycerol, makes it an interesting potential base lubricant. Surprisingly some DESs showed very low corrosion rates with steel, nickel and aluminium even when the liquids contained water. This is a surprising result given that the chloride ion concentration is approximately 5 mol dm−3.

The electrodeposition of aluminium is demonstrated using a eutectic mixture of aluminium chloride and urea. The mixture is shown to be conducting through the formation of both cationic ([AlCl2·urean](+)) and anionic (AlCl4(-)) species and electrodeposition is achieved through the cationic species. The use of a biphasic system with the ionic liquid and a protective hydrocarbon layer allows metal deposition to be carried out in an environment with ambient moisture without the need for a glove box. A direct comparison is made between the AlCl3:urea and imidazolium chloride:AlCl3 systems and the differences in speciation and mass transport manifest themselves in different deposit morphologies. Brighteners which work in the chloroaluminate system such as toluene and LiCl are shown to be ineffective in the urea based system and the reasons for these differences are ascribed to the mechanism of the anodic reaction which is rate limiting.

Biscyclometallated iridium complexes [Ir(ppz)2(X^Y)][PF6] (X^Y = pyridine imine) have been synthesised. The pyridineimine ligands are prepared in situ during the complexation. The complexes show room temperature emission between 640 and 780 nm in CH2Cl2 solution. The emission is red shifted compared with the analogous bipyridine complex [Ir(ppz)2(bipy)][PF6]. DFT calculations have been used to shed light on the influence of the imine substituent on the electrochemical and photochemical properties. In particular, the calculations suggests that there is a significant change in geometry between the ground state and the first triplet excited state for arylimines but not for alkylimines, leading to much weaker emission for the arylimine complexes. The work demonstrates that pyridineimines can be used as a substitute for bipyridines in luminescent iridium complexes.

Electrochemical and transport properties were measured for hydrated chloride salts of copper and tin in ethaline, which is a 1:2 ratio of choline chloride and ethylene glycol. Density, viscosity and conductivity for ethaline melts with different salt concentrations have been measured for temperatures between 293 and 328 K. The change in formal potential with changing metal ion concentration has been determined to evaluate changing speciation in the ionic liquid. Cyclic voltammetry has been carried out to ascertain the reduction potential and diffusion coefficient of the reacting species. For pure ethaline the density was found to decrease by ,5% with increase in temperature. On the other hand, the viscosity was found to decrease and conductivity was found to increase by 65% over the same temperature range. The inclusion of metal salts in ethaline had negligible effect on these parameters. Potential measurements showed that copper was reduced through a two-step mechanism and Sn was reduced via a two electron transfer route. The diffusion coefficient values for Cu 2z and Sn 2z species were 1?22610 211 and 1?96610 211 m 2 s 21 respectively.

The electrodeposition of metals using ionic liquids has received considerable attention during the last ten years. Recent developments have taken these novel electrolytes from laboratory to commercial scale. One of the factors limiting the development into practical plating systems is the understanding of how brighteners function. In this study we describe the addition of three polar additives and their effect upon the nucleation mechanism of zinc and the resultant morphology. It is shown that the structure of the zinc deposits is controlled by double layer properties and it is proposed that the brightening effect of ethylene diamine and ammonia are caused by their ability to inhibit the adsorption of chloride at the electrode surface. The deposition of most metals using ionic liquids results in apparently amorphous deposits, which tend to be actually nano-crystalline. The additives used in this study produce macro-crystalline deposits, which resemble those obtained from aqueous solutions.

In this work the use of glycerol as a hydrogen bond donor in Deep Eutectic Solvents is studied. The physical properties of choline chloride mixtures with glycerol are quantified and it is shown that eutectic mixtures can circumvent some of the difficulties of using glycerol as a solvent viz. high viscosity and high melting point. The solvent properties are characterised using polarity parameters and the values are similar to other ionic liquids although it is shown that this procedure is a poor method of characterising Lewis basicity. The application of these liquids to the esterification of glycerol is used as a demonstration of the ability to tune a reaction with the quaternary ammonium halide acting as a quasi-protecting group. The liquids represent a sustainable way of preparing non-toxic, tuneable solvent systems.

Reported here are results of a systematic study into the electrolytic deposition of Zn metal from ionic liquids based on eutectic mixtures of choline chloride (ChCl) with either ethylene glycol (Eg) or urea. Cyclic voltammetry and gravimetric acoustic impedance spectroscopy (EQCM) techniques have been used to probe mass-transfer and charge-transfer mechanisms. The results show that nucleation in the urea based liquid is fast but bulk growth is slow, whereas nucleation in the glycol based liquid is slow but bulk growth is relatively fast. Critical surface coverage necessary for the transition from nucleation to bulk growth is similar for both liquids. Additionally, ex situ atomic force microscopy (AFM) has been used to probe the morphology of the metallic deposit at two different potentials during a linear sweep voltammogram.

The electrolytic deposition of nickel is demonstrated using a solution of the metal chloride salt separately in either a urea or ethylene glycol/choline chloride based ionic liquid. It is shown that the deposition kinetics and thermodynamics differ from the aqueous processes and these result in different deposit morphologies. It is also shown for the first time that bright metal coatings can be obtained from these liquid systems by adding various brightening agents and deposits can be put directly onto substrates such as aluminium without prior treatment. The general mechanism by which brighteners function in ionic liquids is also discussed.

Ionic liquids are molten salts that have low melting points. This review concentrates upon eutectic mixtures of quaternary ammonium salts and metal salts (usually halides). These so-called eutectic based ionic liquids can be used for the electrodeposition and dissolution of a wide range of metals and alloys. The review highlights the technological challenges involved in the application of ionic liquids to metal finishing.

This work demonstrates that a sustained galvanic coating of silver can be deposited onto copper substrates from a solution of Ag + ions in an ionic liquid (IL) based on a choline chloride (ChCl) eutectic. The sustained growth of the silver deposit was facilitated by the porous nature of the film and is proven using acoustic impedance spectroscopy on a quartz crystal microbalance (QCM). The silver and copper surfaces were characterised using atomic force microscopy (AFM) and scanning electron microscopy (SEM/EDX). In the commercial process of dip coating silver from ions in aqueous media, deposition does not continue once surface coverage has been achieved, without the use of catalysts. The process reported here using ionic liquids produces silver deposits of several microns by dip coating without the use of catalysts or strong inorganic acids.

Eutectic mixtures of zinc chloride and donor molecules such as urea and acetamide are described and it is proposed that these constitute a new class of ionic liquids. FAB-MS analysis shows that the liquids are made up of metal-containing anions and cations in which the donor is coordinated to the cation. Data on the viscosity, conductivity, density, phase behaviour and surface tension are presented and these are shown to be significantly different to other related ionic liquids that incorporate quaternary ammonium salts. The conductivity and viscosity are comparable with other ionic liquids and the data fit well to the Hole theory model recently proposed.

Here we describe the electrolytic deposition of Zn, Sn and Zn/Sn alloys from a solution of the metal chloride salts separately in urea and ethylene glycol/choline chloride based ionic liquids. We show that the deposition kinetics and thermodynamics differ from the aqueous processes and that qualitatively different phases, compositions and morphologies are obtained for the metal coatings in the different ionic liquid systems. We have quantified the electrochemical stripping responses using cyclic voltammetry together with compositional analysis using SEM/EDAX and X-ray diffraction. The differences in electrochemical responses are rationalised in terms of the speciation of both Zn and Sn chlorides in the ionic liquids that have been identified using FAB mass spectrometry. Also we demonstrate that composite metal coatings, e.g. containing Al2O3 particles, can be obtained from these liquid systems by virtue of the stable liquid suspensions. This novel feature of these liquids is a function of their relatively high viscosity.

This paper describes studies of a combined electrochemical/acoustic wave sensor for detection of metal ions in aqueous solutions. The sensor is based upon surface complexation of the metal ions at thiodisuccinic acid (TDS) functionalised self-assembled monolayer (SAM) modified electrodes on 10 MHz AT-cut quartz resonators, functioning as a quartz crystal microbalance (QCM). The SAM-modified electrodes were employed for the detection of Cd(II) ions in single and mixed metal ion solutions, with Pb(II) or Cu(II) as the interferants. Acoustic determination was based on the QCM frequency change associated with the binding to the surface-immobilised ligand of metal ions as a function of their concentration. Frequency response data were acquired under emersed and immersed conditions for ligand binding to the Au electrode and, subsequently, metal ion binding to the ligand. In the latter case, the data were interpreted according to a range of isotherms, of which the Temkin isotherm was found empirically best to describe the concentration dependence. The acoustic wave data yielded information on equilibrium binding stoichiometry and energetics. The extent of metal ion binding was also determined by coulometric assay (upon reduction to the zero-valent metal) after transfer to metal ion-free electrolyte solution. XPS studies of surface-bound metal-TDS ligand complexes confirmed the binding stoichiometry obtained from the electrochemical and acoustic wave responses, and provided information on the ligand–substrate binding and bound analyte oxidation state.

We demonstrate the first practical alternative to the use of phosphoric and sulphuric acid mixtures for the electropolishing of stainless steel. In this paper, efficient electropolishing of type 316 stainless steel is demonstrated in an ionic liquid composed of ethylene glycol (HOCH2CH2OH) and choline chloride (HOC2H4N(CH3)3+Cl−). Linear sweep voltammetry, chronoamperometry, scanning electron microscopy, atomic force microscopy and AC impedance methods were used to investigate the steel dissolution mechanism and the results are compared to polishing done in aqueous acidic solutions. It is shown that the quality of the polish is related to the breakdown of the oxide film and preliminary data suggest that the polishing process may be controlled by the diffusion of chloride ions. The dissolution is different from that found in aqueous acid solutions, and oxide breakdown is shown to be slower, which can lead to pitting at low current densities.

The addition of a simple amide to AlCl(3) causes the formation of a liquid of the form [AlCl(2)·nAmide](+) AlCl(4)(-). The material thus produced is liquid over a wide temperature range, is relatively insensitive to water and has the properties of an ionic liquid. This ionic liquid is shown to be a suitable medium for the acetylation of ferrocene and the electrodeposition of aluminium and demonstrated that quaternary ammonium cations are not always needed to form ionic liquids.

Cyclometallated phenyls with substituents para to the metal have a larger impact on the redox potentials and emission of complexes [Ir(R-ppz)(2)(bipy)][PF(6)] than substituents at the meta position and hence enable tuning of emission wavelength over a wider range using the same substituent.

Here we describe for the first time the electrolytic deposition of copper and copper composites from a solution of the metal chloride salt in either urea–choline chloride, or ethylene glycol–choline chloride based eutectics. We show that the deposition kinetics and thermodynamics are quite unlike those in aqueous solution under comparable conditions and that the copper ion complexation is also different. The mechanism of copper nucleation is studied using chronoamperometry and it is shown that progressive nucleation leads to a bright nano-structured deposit. In contrast, instantaneous nucleation, at lower concentrations of copper ions, leads to a dull deposit. This work also pioneers the use of the electrochemical quartz crystal microbalance (EQCM) to monitor both current efficiency and the inclusion of inert particulates into the copper coatings. This technique allows the first in situ quantification or particulate inclusion. It was found that the composition of composite material was strongly dependent on the amount of species suspended in solution. It was also shown that the majority of material was dragged onto the surface rather than settling on to it. The distribution of the composite material was found to be even throughout the coating. This technology is important because it facilitates deposition of bright copper coatings without co-ligands such as cyanide. The incorporation of micron-sized particulates into ionic liquids has resulted, in one case, in a decrease in viscosity. This observation is both unusual and surprising; we explain this here in terms of an increase in the free volume of the liquid and local solvent perturbation.

This Chapter reviews the area of inorganic complexes in ionic liquids. It focuses primarily on the literature published during the calendar year 2007 but more generally it discusses the lack of information and the problems associated with collecting data in these solvents. The applications in which inorganic complexes play a vital role are highlighted in this review together with the importance that speciation plays in controlling the chemistry of metal ions.

The electrochemical quartz crystal microbalance was used to determine redox-driven ion transfers accompanying p-doping of polypyrrole (PPy) films in the choline chloride-based deep eutectic ionic liquid ethaline; electroneutrality maintenance is gravimetrically dominated by choline cation transfer and this requires the presence within the undoped film of ionic liquid, when this finite reservoir of choline is exhausted there is a shift to chloride transfer.

We describe in situ neutron reflectivity (NR) and RAIRS studies of the chemical modification of films of a polypyrrole-based conducting polymer derived from the pentafluorophenyl ester of poly(pyrrole-N-propanoic acid) (PFP) electrodeposited on electrode surfaces. We explore the role of the solvent in controlling the rate of reaction with solution-based nucleophiles (amines, which react with the ester to form amides). By varying the identity of the solvent (water vs acetonitrile) and the neutron contrast (deuteration), we find that both the identity of the solvent and its population within the film are paramount in determining chemical reactivity and electroactivity. IR signatures allow monitoring of the reaction of solution-based amine-tagged species such as amino-terminated poly(propylene glycol), ferrocene ethylamine, and lysine with film-based ester functionalities: the carbonyl bands show ester/amide interconversion and some hydrolysis to acid. Time-dependent spectral analysis shows marked variations in reaction rate with (i) (co-)polymer composition (replacement of some fluorinated ester-functionalized pyrrole with unfunctionalized pyrrole), (ii) the solvent to which the polymer film is exposed, and (iii) the rate of polymer deposition. NR data provide solvent profiles as a function of distance perpendicular to the interface, the variations of which provide an explanation for film reactivity patterns. Homopolymer films are relatively hydrophobic, thus hindering reaction with species present in water solutions. Incorporating pyrrole groups raises the solvent population-dramatically for water-thereby facilitating entry and reaction of aqueous-based lysine. Changing film deposition rate yields films with different absolute levels of solvent and reactivity patterns that are dependent on the size of the reactant molecules: more rapid deposition of polymer gives films with a more open structure leading to a higher solvent content and thence increased reactivity. These results, supported by XPS and AFM data, allow assembly of composition-structure-reactivity correlations, in which the controlling feature is film solvation.

The electrodeposition of chromium is a technologically vital process, which is principally carried out using aqueous chromic acid. In the current study, it is shown that eutectic mixtures of urea and hydrated chromium(III) chloride provide a liquid which reduces the toxicological issues associated with the current aqueous Cr(VI) electroplating solution. Using EXAFS, mass spectrometry and UV-Vis spectroscopy, it is shown that chromium is present predominantly as a cationic species. Conductivities are higher than for most comparable ionic liquids. It is shown that the electrodeposition of chromium is electrochemically reversible, with a current efficiency much higher than in aqueous electrolytes. Surface tension and density measurements indicate that hole theory is a valid model to describe transport properties in these liquids. Bulk Cr deposits are not macrocrystalline but they are generally crack-free. The deposits have a hardness of 600 ± 10 Vickers and, as such, are comparable to deposits from aqueous systems.

The first electrochemical series in a deep eutectic solvent (DES) is described. Speciation resulting from the unusual chemistry of the choline chloride based DES is used to explain both similarities and differences from aqueous media. We give examples of how these differences can be exploited in technologically important systems.

The electrodeposition of zinc has been studied in two deep eutectic solvents. Unlike the metals studied to date in these liquids, zinc electrodeposition is not mass transport limited and the morphology of the deposit differs in the two liquids. This study shows that changing the concentration of solute affects the physical properties of the liquid to different extents although this is found to not effect the morphology of the metal deposited. EXAFS was used to show that the speciation of zinc was the same in both liquids. Double layer capacitance studies showed differences between the two liquids and these are proposed to be due to the adsorption of a species on the electrode which is thought to be chloride. The differences in zinc morphology is attributed to blocking of certain crystal faces leading to deposition of small platelet shaped crystals in the glycol based liquid.

This Chapter reviews the area of inorganic complexes in ionic liquids. It focuses primarily on the literature published during the calendar year 2007 but more generally it discusses the lack of information and the problems associated with collecting data in these solvents. The applications in which inorganic complexes play a vital role are highlighted in this review together with the importance that speciation plays in controlling the chemistry of metal ions.

Here we demonstrate the generation of novel ionic liquid analogue (ILA) electrolytes for aluminium (Al) electrodeposition that are based on salts of amidine Lewis bases. The electrolytes exhibit reversible voltammetric plating/stripping of Al, good ionic conductivities (10–14 mS cm−1), and relatively low viscosities (50–80 cP). The rheological properties are an improvement on analogous amide-based ILAs and make these liquids credible alternatives to ILAs based on urea or acetamide, or conventional chloroaluminate ionic liquids (IL) for Al battery applications.

Protonation of trans-[W(N2)2(Ph2PCH2CH2PPh2)2] with toluene-p-sulphonic acid gives the hydrazido cation trans-[W(NNH2)(p-MeC6H4SO3)(Ph2PCH2CH2PPh2)2]+. Reduction of this cation at a Hg-pool electrode in a tetrahydrofuran electrolyte under N2(1 atm) affords free ammonia with regeneration of the parent dinitrogen complex in excellent yield. Protonation of the regenerated product allows the system to be cycled and this can be performed in one vessel, the cathode compartment of the electrolysis cell.

In this paper, we explore the role that polymer conductivity and functionality play in determining the nature of molecular recognition at artificial polymer interfaces, as evidenced by electron transfer with the small redox protein, cytochrome c . The relationship is investigated electrochemically using cyclic voltammetry in order to assess the degree of molecular recognition between the biological molecule and carboxyl-functionalized β -substituted poly(thiophenes) and poly(pyrroles), as well as a co-polymer matrix of these derivatives. In the latter case, the co-polymer film was analysed quantitatively using X-ray photoelectron spectroscopy, and it was found that its composition did not reflect the initial molar ratios of the monomers prior to electrodeposition.

We show that the amperometric response of redox couples can be amplified at electrodes covered with microcrystalline solids and the corollary, that the electrorelease of surface materials can be triggered by solution molecules.

Protonation of trans-[W(N2)2(Ph2PCH2CH2PPh2)2] with toluene-p-sulphonic acid gives the hydrazido cation trans-[W(NNH2)(p-MeC6H4SO3)(Ph2PCH2CH2PPh2)2]+. Reduction of this cation at a Hg-pool electrode in a tetrahydrofuran electrolyte under N2(1 atm) affords free ammonia with regeneration of the parent dinitrogen complex in excellent yield. Protonation of the regenerated product allows the system to be cycled and this can be performed in one vessel, the cathode compartment of the electrolysis cell.