Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes.     

Calcium Carbonate Dissolution from the Laboratory to the Ocean: Kinetics and Mechanism

The ultimate fate, over the course of millennia, of nearly all of the carbon dioxide formed by humankind is for it to react with calcium carbonate in the world's oceans. Although, this reaction is of global relevance, aspects of the calcite dissolution reaction remain poorly described with apparent contradictions present throughout the expansive literature. In this perspective we aim to evidence how a lack of appreciation of the role of mass-transport may have hampered developments in this area. These insights have important implications for both idealised experiments performed under laboratory conditions and for the measurement and modelling of oceanic calcite sediment dissolution.     

A flow system for hydrogen peroxide production at reticulated vitreous carbon via electroreduction of oxygen

In this work, a reticulated vitreous carbon electrode (RVCE, 96.5 % porosity, 24 cm^?1) was modified with 2-anthraquinonyl groups to electrocatalytically reduce dissolved oxygen in neutral aqueous solution (0.1 M phosphate buffer solution supported with 3 M potassium chloride, pH of 6.7) to hydrogen peroxide (H₂O₂) at 25 °C under atmospheric pressure. The obtained current density was ca. 3 mA cm^?2. For the first time, the oxygen reduction was investigated on a novelly designed RVCE housed in a gravity-feed flow system. Fractional current conversions obtained on the RVC flow cell were compared and contrasted with those on a two-dimensional electrode, viz. a tubular flow electrode. The modified-on catalyst has the benefit in terms of easy separation of the product from the catalyst. The in situ generated low concentration of H₂O₂ provides potential applications to water purification processes and disinfection for water and food.     

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. This is to the authors knowledge the first system to exhibit a phase transition of an adsorbed species on a boron doped diamond surface. At low scan rates the system is found to oscillate; these oscillations are ascribed to the presence of a 'negative differential resistance'.     

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. Accordingly a large array of voltammetric methods ultimately aimed at making cheap and most likely disposable electrodes have been reported. This critical review analyses the context in which physiological glutathione measurement can be undertaken electrochemically and compares it to current assay approaches, while also covering the current literature for glutathione disulfide detection. The various characteristics and limitations of the methodologies are compared and contrasted, with the analytical parameters (matrix, pH, limit of detection, etc.) tabulated to aid comparison.     

A simplified methodology: pH sensing using an in situ fabricated Ir electrode under neutral conditions

Herein, a simplified fabrication method for the producing of a pH-sensitive iridium electrode is developed. The in situ electrochemical fabrication of an iridium oxide film is optimized and shown to be achievable under neutral conditions rather than the acidic conditions hitherto employed. The formation of a pH sensitive Ir(III/IV) hydrous film is confirmed via XPS. The amperometric pH-sensing properties of this electrochemically generated material were investigated using square wave voltammetry. In the pH range 2–13, the iridium oxide redox signal has a pH dependency of 86.1 ± 1.1 mV per pH unit for midpoint potentials with uncertainties being ± 0.01–0.05 pH. Finally, the newly developed pH sensor was used to measure the pH of a natural water sample with excellent results as compared to a conventional glass pH probe.

     

The electroanalytical detection of hydrazine: a comparison of the use of palladium nanoparticles supported on boron-doped diamond and palladium plated BDD microdisc array

We show that both a random distribution of palladium nanoparticles supported on a BDD electrode or a palladium plated BDD microelectrode array can each provide a sensing platform for the electrocatalytic detection of hydrazine. The palladium nanoparticle modified electrode displays a sensitivity and limit of detection of 60 mA mol(-1) L and 2.6 microM respectively while the array has a sensitivity of 8 mA mol(-1) L with a detection limit of 1.8 microM. The beneficial cost implications of using palladium nano- or micro-particles in sensors compared to a palladium macroelectrode are evident. Interestingly the array of the nanoparticles shows similar sensitivity and limit of detection to the microelectrode array which probably indicates that the random distribution of the former leads to 'clumps' of nanoparticles that effectively act as microelectrodes.     

Controlling voltammetric responses by electrode modification; using adsorbed acetone to switch graphite surfaces between adsorptive and diffusive modes

Graphite is a highly versatile electrode substrate material but the recorded voltammetric response is regularly complicated by varying degrees of adsorption of the analyte to the surface leading to voltammetry which is complex to analyse. We report how through the pre-adsorption of acetone the electro-activity of the substrate is unhindered but adsorption of an electro-active species is effectively blocked, hence the experimentalist is able to readily tailor the electrode so as to effectively switch the adsorption of the analyte 'on' or 'off'.     

The influence of substrate effects when investigating new nanoparticle modified electrodes exemplified by the electroanalytical determination of aspirin on NiO nanoparticles supported on graphite

The apparent electrocatalytic detection of aspirin and salicylic acid is compared using NiO nanoparticles and microparticles supported on graphitic electrodes using abrasive and non-abrasive (drop-dry) immobilisation. However control experiments revealed that, the observed voltammetry is not due to the immobilised NiO materials, but is instead due to the underlying graphitic substrates. Abrasive immobilisation of NiO microparticles on a graphite electrode abrades the underlying electrode surface, introducing more electroactive edge-plane defects. Even when drop-dry immobilisation is used (i.e. non-abrasive), appropriate control experiments are still required as other experimental methods employed may change the nature of the underlying substrate.     

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). The simulation of cyclic voltammograms involving the distribution of formal potentials showed a better fit than the simulation with the distribution of tunneling distances. Importantly the reorganization energies used for the simulation of E' distribution were similar to the literature values for adsorbed species.