Formic acid electro-synthesis from carbon dioxide in a room temperature ionic liquid.

The novel synthesis of formic acid has been achieved in a room temperature ionic liquid via the reaction of electro-activated carbon dioxide and protons on pre-anodised platinum. Only mild reaction conditions of room temperature and 1 atm CO(2) were used. This work highlights the effect of pre-anodisation on Pt surfaces.

Tuning solute redox potentials by varying the anion component of room temperature ionic liquids.

The electrode potentials for the two one electron oxidations of 1,2-diferrocenylethylene (bisferrocene, BF) were studied relative to that of the one electrode oxidation of decamethylferrocene in a variety of RTILs. The difference in these potentials was found to be very sensitive to the anion component of the ionic liquid showing the scope of these solutes as 'designer media' to tune the thermodynamic properties of solutes dissolved in them.

An electrochemical thermometer: voltammetric measurement of temperature and its application to amperometric gas sensing.

We report a temperature sensing system incorporated into an amperometric oxygen sensor. In the first part of this work, we introduce temperature sensing systems based upon voltammetric responses of both single molecule (1,2-diferrocenylethylene in 1-propyl-3-methylimidazolium bistrifluoromethylsulfonylimide) and two independent molecules (decamethylferrocene and N,N,N',N'-tetramethyl-p-phenylenediamine in 1-ethyl-3-methylimidazolium tetracyanoborate) respectively. In both systems, the difference in the formal potentials of two redox centres was measured as a function of temperature.

The formal potentials and electrode kinetics of the proton/hydrogen couple in various room temperature ionic liquids.

The Hydrogen evolution reaction has been quantitatively investigated at a Pt electrode in series of room temperature ionic liquids vs. Ag/Ag(+) redox couple. The measured formal potentials of the H(2)/H(+) (HNTf(2)) redox couple in each RTIL reveals a dependence on the nature of anion, suggesting significant interaction between proton and anion.

The theory of cyclic voltammetry of electrochemically heterogeneous surfaces: comparison of different models for surface geometry and applications to highly ordered pyrolytic graphite.

The cyclic voltammetry at electrodes composed of multiple electroactive materials, where zones of one highly active material are distributed over a substrate of a second, less active material, is investigated by simulation. The two materials are assumed to differ in terms of their electrochemical rate constants towards any given redox couple. For a one-electron oxidation or reduction, the effect on voltammetry of the size and relative surface coverages of the zones as well as the rate constant of the slower zone are considered for systems where it is much slower than the rate constant of the faster zones.

Electrochemical determination of glutathione: a review.

The physiological importance of glutathione and glutathione disulfide is evident from their implications in an array of medical conditions including diabetes, Parkinson's disease and cancer. As such the need for simple, rapid and cheap assays to aid clinical diagnostics and treatment is clear. These requirements are, in principle at least, ideally suited to electrochemical detection.

One-step synthesis of fluorescein modified nano-carbon for Pd(II) detection via fluorescence quenching.

Carbon black (CB) nanoparticles modified with fluorescein, a highly fluorescent molecule, were prepared using a facile and efficient methodology. Simply stirring CB in aqueous solution containing fluorescein resulted in the strong physisorption of fluorescein onto the CB surface. The resulting Fluorescein/CB was then characterised by means of X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), fluorescence microscopy and fluorescence spectroscopy.

The hydrogen evolution reaction in a room temperature ionic liquid: mechanism and electrocatalyst trends.

The kinetics and mechanism of the proton reduction reaction in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf(2)]) was studied at gold, molybdenum, nickel, titanium and platinum electrodes. Significant differences in electrochemical rate constants were observed between the different metals and with the corresponding processes in aqueous solution. The hydrogen evolution mechanism was consistent at all five metals in the ionic liquid, in stark contrast to the known behaviour in aqueous systems.

Electrode kinetics at carbon electrodes and the density of electronic states.

Marcus-Hush theory relates the rate of electron transfer to the density of electronic states of the electrode material. Through use of a carbon microelectrode--for which the density of states is expected to vary as a function of potential--this predication is validated for graphitic materials by measurement of a variety of outer-sphere redox systems.

The electrochemical detection of tagged nanoparticles via particle-electrode collisions: nanoelectroanalysis beyond immobilisation.

The use of particle-impact coulometry in identifying and quantifying nanoparticles tagged (or labelled) with electroactive molecules is demonstrated via the detection of 1,4-nitrothiophenol-tagged silver nanoparticles in aqueous dispersion at potentials more negative than -0.17 V (vs. Ag/AgCl, the reduction potential of nitrothiophenol) via monitoring of particle-electrode collisions.

Generator-collector double electrode systems: a review.

A variety of generator-collector systems are reviewed, from the original rotating ring-disc electrodes developed in the 1950s, to very recent developments using new geometries and microelectrodes. An overview of both theoretical and experimental aspects are given, and the power of these double electrode systems in analytical electrochemistry is illustrated with a range of applications.

The adsorption of quinizarin on boron-doped diamond.

The voltammetric response of the quinone species 'quinizarin' (QZ) and its electrocatalytic reduction of oxygen are studied at a boron doped diamond electrode (BDD). It is demonstrated that, contrary to the widespread belief that adsorption of organic molecules on BDD is minimal, not only does QZ readily adsorb to the electrodes surface but this adsorption is also influenced at low surface coverages by the pre-exposure of the electrode to organic solvents. Furthermore, the nature of this adsorbed QZ species is investigated and a potential dependent phase transition is observed.

Mass transport to micro- and nanoelectrodes and their arrays: a review.

The use of micro- and nanoelectrodes and their arrays has become commonplace in modern electrochemistry. Numerical simulation is often required for detailed analysis of voltammetric data and this relies upon an understanding of the prevailing mass transport operating under the experimental conditions. The theoretical basis of our understanding of mass transport, particularly diffusion and migration, has developed greatly in recent years.

The electrochemistry of quinizarin revealed through its mediated reduction of oxygen.

After 35 years the hunt for improved anthracycline antibiotics is unabated but has yet to achieve the levels of clinical success desired. Electrochemical techniques provide a large amount of kinetic and thermodynamic information, but the use of such procedures is hindered by issues of sensitivity and selectivity. This work demonstrates how by harnessing the mechanism of catalytic reduction of oxygen by the quinone functionality present within the anthracycline structure it is possible to study the reactive moiety in nanomolar concentration.

New chemical insights using weakly supported voltammetry: ion pairing in the EC2 reduction of 2,6-diphenylpyrylium in acetonitrile.

Pairing effect: Varying the concentration of support electrolyte in the electrochemical EC(2) reduction of 2,6-diphenylpyrylium reveals the presence of ion pairing between the electroactive species and BF(4)(-). Experiment and theory are shown to be in good agreement only if ion pairing is included in the simulations. This previously unanticipated effect is only observable if voltammetry is performed under conditions of weak support.

Gold nanoparticles show electroactivity: counting and sorting nanoparticles upon impact with electrodes.

Gold nanoparticles (AuNPs) in aqueous 0.10 M HCl are shown to be electroactive at oxidising potentials greater than 1.0 V (vs.

Edge plane pyrolytic graphite electrode covalently modified with 2-anthraquinonyl groups: theory and experiment.

An edge plane pyrolitic graphite (EPPG) electrode was modified by electrochemical reduction of anthraquinone-2-diazonium tetrafluoroborate (AQ2-N(2)(+)BF(4)(-)), giving an EPPG-AQ2-modified electrode of a surface coverage below a monolayer. Cyclic voltammograms simulated using Marcus-Hush theory for 2e(-) process assuming a uniform surface gave unrealistically low values of reorganisation energies, λ, for both electron transfer steps. Subsequently, two models of surface inhomogeneity based on Marcus-Hush theory were investigated: a distribution of formal potentials, E', and a distribution of electron tunneling distances, r(0).

Electrolyte tuning of electrode potentials: the one electron vs. two electron reduction of anthraquinone-2-sulfonate in aqueous media.

The electrode potentials of quinone redox centres in aqueous solutions can be tuned by varying the electrolyte cation identity. The phenomenon is due to the ion pairing effect of the tetra-n-butylammonium cation with the semiquinone intermediate species.

Dynamics of ion transfer potentials at liquid-liquid interfaces: the case of multiple species.

The dynamic evolution of a water-nitrobenzene system with both solvents containing an initially equimolar mixture of two monovalent binary electrolytes, sharing a common cation, is simulated using the Nernst-Planck-Poisson finite difference method. The effect of single ion partition coefficients and diffusion coefficients on the evolution of potential across the liquid-liquid interface is investigated. Two separable components of the potential difference are observed: a static component localized at the liquid-liquid interface and a diffuse component with dynamic spatial expansion.

Analytical theory of the catalytic mechanism in square wave voltammetry at disc electrodes.

A simple analytical expression is presented for the study of the first-order catalytic mechanism using Square Wave Voltammetry (SWV) at disc electrodes. These electrodes are extensively used in electrochemical studies but modelling the electrochemical response at this geometry is complex and usually requires the use of sophisticated numerical methods. By contrast, the analytical solution presented in this work is easy to compute and it is applicable to any size of the disc and for arbitrary kinetics of the catalytic reaction.

Increased sensitivity of anodic stripping voltammetry at the hanging mercury drop electrode by ultracathodic deposition.

An improved approach to the anodic stripping voltammetric (ASV) determination of heavy metals, using the hanging mercury drop electrode (HMDE), is reported. It was discovered that using very cathodic accumulation potentials, at which the solvent reduction occurs (overpotential deposition), the voltammetric signals of zinc(II), cadmium(II), lead(II) and copper(II) increase. When compared with the classical methodology a 5 to 10-fold signal increase is obtained.

Catalytic mechanism in cyclic voltammetry at disc electrodes: an analytical solution.

The theory of cyclic voltammetry at disc electrodes and microelectrodes is developed for a system where the electroactive reactant is regenerated in solution using a catalyst. This catalytic process is of wide importance, not least in chemical sensing, and it can be characterized by the resulting peak current which is always larger than that of a simple electrochemical reaction; in contrast the reverse peak is always relatively diminished in size. From the theoretical point of view, the problem involves a complex physical situation with two-dimensional mass transport and non-uniform surface gradients.

Nanoparticle-electrode collision processes: the underpotential deposition of thallium on silver nanoparticles in aqueous solution.

The electrochemistry of collisions between metal nanoparticles (NPs) and electrode surfaces has been of recent interest with the development of anodic particle coulometry as a characterisation method. For the first time the underpotential deposition of metal ions from solution onto metal nanoparticles during collisions between the NPs and an inert electrode is reported.