The electrocatalytic and stoichiometric oxidation chemistry of binuclear ruthenium complexes incorporating the anionic tripod ligand {(η5-C5H5)Co[P(OCH3)2(=O)]3}-

The anionic tripod ligand NaLoMe (L_(oMe) - = [(η^5-C_5H_5)Co{P(O)(OCH_3)_2}_3]^-) reacts with RuO_4 in a biphasic reaction mixture of 1% H_2SO_4 and CCI_4 to afford [(L_(oMe) (HO)Ru^(IV) (µ-O)_2Ru ^(IV)(OH)(L_(oMe)] (1), which is treated with aqueous CF_3S0_3H to generate [(L_(oMe)(H_2O)Ru^(IV) (µ-O)_2R^(IV) (OH_2)(L_(oMe)][CF_3SO_3]_2 ([H_21][CF_3SO_3]_2). Addition of iodosobenzene to an acetonitrile solution of this salt yields [(L_(oMe)(O)Ru^v(µ-0)2Ru^v-(O)(_(LoMe)] (2). The dimer 1 can be reduced chemically or electrochemically to the Ru^(III)- Ru^(III) dimers [(L_(oMe)(H_20)Ru^(III) (µ-OH)_2Ru^(III) (OH_2)(L_(oMe)) ]^2+ and [(L_(oMe)) ^(III) (µ-0Hh(µ-0H2)Ru^(III) (L_(oMe)]^2+ which interconvert in aqueous media. Two electron processes dominate both the bulk chemistry and the electrochemistry of 1. Among these processes are the quasi-reversible Ru^(IV) - Ru^(IV)/Ru^(III)- Ru^(III) and Ru^(III)- Ru^(III)/ Ru^(II)- Ru^(II) reductions and a largely irreversible Ru^(V) - Ru^(V)/ Ru^(IV) - Ru^(IV)/oxidation. The dioxo dimer 2 oxidizes alcohols and aldehydes in organic media to afford 1 and the corresponding aldehydes and acids. Analogously, the Ru^(V) - Ru^(V)/ Ru^(IV)- Ru^(IV) redox wave mediates the electrooxidation of alcohols and aldehydes in aqueous buffer. In this system, substrates can be oxidized completely to CO_2. The kinetic behavior of these oxidations was examined by UV-vis and chronoamperometry, respectively, and the chemistry is typical of metal-oxo complexes, indicating that electronic coupling between two metal centers does not dramatically affect the metal-oxo chemistry. Dimer [H_21]^(2+) also reacts with alcohols, aldehydes, and triphenylphosphine in CH_3CN to afford Ru^(III)- Ru^(III) products including [(L_(oMe))CH_3CN) Ru^(III) (µ-OH)_2 Ru^(III) (NCCH_3)( L_(oMe))][CF_3SO_3]2 (characterized by X-ray crystallography) and the corresponding organic products. Reaction of 1 with formaldehyde in aqueous buffer quantitatively affords the triply bridged dimer [(L_(oMe)Ru^(III) (µ-OH)2- (µ-HCOO) Ru^(III) (L_(oMe)][CF_3SO_3] (characterized by X-ray crystallography). This reaction evidently proceeds by two parallel inner-sphere pathways, one of which is autocatalytic. Neither pathway exhibits a primary isotope effect suggesting the rate determining process could be the formation of an intermediate, perhaps a Ru^(IV) - Ru^(IV) formate adduct. The Ru^(III)- Ru^(III)formate adduct is easily oxidized to the Ru^(IV) - Ru^(IV) analog [(L_(oMe)Ru^(IV)(µ-OH)_2-(µ-HCOO) Ru^(IV) (L_(oMe)][CF_3SO_3], which, after isolation, reacts slowly with aqueous formaldehyde to generate free formate and the Ru^(III)- Ru^(III) formate adduct. These dimers function as catalysts for the electrooxidation of formaldehyde at low anodic potentials (+0.0 V versus SCE in aqueous buffer, pH 8.5) and enhance the activity of Nafion treated palladium/carbon heterogeneous fuel cell catalysts.

A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

In-situ FT-IR spectroscopic studies of fuel cell electro-catalysis: From single-crystal to nanoparticle surfaces

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO+(2x2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1x1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20 degrees C, the adsorbed CO is present as rather compact islands. In contrast, at 60 degrees C, the COads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of COads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO2. Increasing temperature from 20 to 60 degrees C significantly facilitates the methanol turnover to CO2.

Susceptibility to stress corrosion cracking of NiTi laser weldment in Hanks’ solution

In this study, the susceptibility to stress corrosion cracking (SCC) of laser-welded NiTi wires in Hanks’ solution at 37.5 °C was studied by the slow strain-rate test (SSRT) at open-circuit potential and at different applied anodic potentials. The weldment shows high susceptibility to SCC when the applied potential is near to the pitting potential of the heat-affected zone (HAZ). The pits formed in the HAZ become sites of crack initiation when stress is applied, and cracks propagate in an intergranular mode under the combined effect of corrosion and stress. In contrast, the base-metal is immune to SCC under similar conditions. The increase in susceptibility to SCC in the weldment could be attributed to the poor corrosion resistance in the coarse-grained HAZ.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

On the electrochemical behavior of Cu-16%Zn-6.5%Al alloy containing the β'-phase (martensite) in borate buffer

In this work, the electrochemical behavior of Cu-16(wt.%)Zn-6.5(wt.%)Al alloy containing the β'-phase (martensite) was studied in borate buffer solution (pH 8.4) by means of open-circuit potential (EOC), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The alloy EOC was -0.29 V vs. Hg/HgO/OH-, similar to that of pure copper in this medium, indicating that the processes which occur on the alloy surface are mainly governed by copper. EIS response was related to the dielectric and transmission properties of the complex oxide layer. The CVs showed peaks concerning the redox reactions for copper and zinc. These peaks were assigned to the formation and reduction of copper and zinc species. Furthermore, they showed that the copper oxidation was suppressed by the presence of zinc and aluminum in the alloy composition. The copper and zinc oxidation to form complex oxide layers and the reduction of the different metallic oxides generated in the anodic potential scan suggest that a solid state reaction could determine the metallic oxide formation. © 2013 Elsevier Ltd. All rights reserved.

Tribocorrosion response of the Ti6Al4V alloys commonly used in femoral stems

In prosthesis, tribochemical reactions occur at the stem/bone interface. When coupled with micromotions it can lead to the loosening of the implant, osteolysis, release of metal ion and wear particles. The effect of these movements and the underlying mechanisms are quite unknown. This work investigates the tribocorrosion behavior of etched Ti6Al4V alloys under reciprocating sliding. Tests were performed in a phosphate buffer solution (PBS) containing proteins. A normal load of 1 N and anodic potentials of -0.1 and +0.5 V/SCE were applied. The destruction pathways of the top surface layers (adsorbed proteins, passive film) were studied. The results showed that the favorable/undesired effect of proteins in solution depends on the characteristics of the passive film under a mechanical stress. (C) 2013 Elsevier Ltd. All rights reserved.

Structure and dynamics of ionic liquid,electrode interfaces

In the early 20th century, Gouy, Chapman, and Stern developed a theory to describe the capacitance and the spatial ion distribution of diluted electrolytes near an electrode. After a century of research, considerable progress has been made in the understanding of the electrolyte/electrode interface. However, its molecular-scale structure and its variation with an applied potential is still under debate. In particular for room-temperature ionic liquids, a new class of solventless electrolytes, the classical theories for the electrical double layer are not applicable. Recently, molecular dynamics simulations and phenomenological theories have attempted to explain the capacitance of the ionic liquid/electrode interface with the molecular-scale structure and dynamics of the ionic liquid near the electrode. rnHowever, experimental evidence is very limited. rnrnIn the presented study, the ion distribution of an ionic liquid near an electrode and its response to applied potentials was examined with sub-molecular resolution. For this purpose, a new sample chamber was constructed, allowing in situ high energy X-ray reflectivity experiments under potential control, as well as impedance spectroscopy measurements. The combination of structural information and electrochmical data provided a comprehensive picture of the electric double layer in ionic liquids. Oscillatory charge density profiles were found, consisting of alternating anion- and cation-enriched layers at both, cathodic and anodic, potentials. This structure was shown to arise from the same ion-ion correlations dominating the liquid bulk structure that were observed as a distinct X-ray diffraction peak. Therefore, existing physically motivated models were refined and verified by comparison with independent measurements. rnrnThe relaxation dynamics of the interfacial structure upon potential variation were studied by time resolved X-ray reflectivity experiments with sub-millisecond resolution. The observed relaxation times during charging/discharging are consistent with the impedance spectroscopy data revealing three processes of vastly different characteristic time-scales. Initially, the ion transport normal to the interface happens on a millisecond-scale. Another 100-millisecond-scale process is associated with molecular reorientation of electrode-adsorbed cations. Further, a minute-scale relaxation was observed, which is tentatively assigned to lateral ordering within the first layer.

The electrochemical surface forces apparatus : the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at similar to 0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO3 during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO3 inside of the TiO2 surface layer seems to be constant. (c) 2006 Elsevier Ltd. All rights reserved.

Occurrence of anodic current and corrosion of steel in aqueous media under fluctuating cathodic protection potentials

Excursion of cathodic protection (CP) potential from the designed "safe" CP level resulting from various forms of electrical interference signals are observed rather frequently in industrial applications, in particular in the pipeline industry; however, the influence of such potential fluctuations on the corrosion behavior of steel under CP conditions does not yet appear to be fully understood. In this work, the effects of anodic transients that periodically shift the potential of a CP protected steel electrode from-1,200 mVAg/AgCl to-750 mVAg/AgCl on the corrosion of a steel electrode in aqueous media was investigated using square wave polarization. Anodic currents were measured that lasted for significant periods of time upon stepping the CP potential up to a less cathodic potential at various frequencies (1 h, 30 s, 10 s, 5 s, and 1 s). Part of such anodic currents is found to cause steel corrosion, and this is explained on the basis of understanding the Fe/H2O equilibrium.

Potentiodynamic behaviour of β-lead dioxide in neutral media at positive potentials

The behaviour of the PbO2 electrode in NaNO3, Na2SO4 NaClO4 and NaCl in the pH range 3.0–10.5 has been studied by cyclic voltammetry. When the electrode is cycled between 0.30 and 1.90 V, a large cathodic current peak appears in the negative scan; in the subsequent cycle, two anodic peaks appear. The addition of H2O2 at low concentrations to the electrolyte also results in two anodic peaks at the same potentials. A number of possible explanations for the appearance of the cathodic peak, and a mechanism for the oxidation of PbO to PbO2 through Pb3O4 corresponding to the two anodic peaks, are proposed.

Role of applied potentials on bioleaching of chalcopyrite concentrate and growth of Acidithiobacillus ferrooxidans

The effect of applied DC potentials on the bioleaching of a chalcopyrite concentrate in the presence of Acidithiobacillus ferrooxidans is discussed. Copper dissolution was the highest at an applied potential of +600mV (SCE), while all the dissolved copper got cathodically deposited at a negative potential of -600mV (SCE). Electrobioleaching at an applied potential of +600mV (SCE) was established at different pulp densities as a function of time. The effect of applied potentials and electrolytic currents on the activity and growth of bacterial cells was assessed Preadaptation of bacterial cells to the concentrate slurry and electrolytic growth conditions significantly enhanced copper dissolution. Electrochemical and biochemical mechanisms involved in electrobioleaching are illustrated with respect to oxidative dissolution and biocatalysis of anodic oxidation.

Anodic voltammetric behavior of inosine on a glassy carbon electrode

The anodic voltammetric behavior of inosine (I) was investigated by linar-sweep voltammetry, differential-pulse voltammetry and cyclic voltammetry at a glassy carbon electrode. In a medium of 0.1 mol/L N2HPO4, inosine showed a well defined anodic peak. The peak potential was about 1.42 V (vs. Ag/AgCl). A linear relationship held between the peak current and the concentration of inosine in the rang of 5 x 10(-4) similar to 8 x 10(-2) g/L. The peak potential decreased with the decrease of the acidity of the solution. The four anodic peaks of inosine with hypoxanthine, xanthine and uric acid were obtained. Their peak potentials were about at 1.42, 1.07, 0.72 and 0.26 Vt vs. Ag/AgCl). The method has been used for the direct determination of inosine in injections. Recoveries of inosine in urine samples were about 85%. Experimental result proved that the electrode reaction was diffusion-controlled and irreversible.

Effects of spark discharge on the anodic coatings on magnesium alloy

Spark discharge was the representative phenomenon of Micro-arc oxidation (MAO) method distinguished from other electrochemical oxidation methods. Under the spark discharge treatment, characteristics of the anodic layer were significantly changed. To investigate the influences of the spark discharge, a piece of magnesium alloy AZ91D specimen was partly treated by MAO method in alkaline silicate solution. And the microstructure, element distributions as well as the surface potential distributions of the specimen were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and scanning Kelvin probe (SKP) technique. As a result of intensive spark discharge treatment, porous external layer with dense internal layer were formed on Mg alloy surface. At the same time, the depositions of OH- and SiO32- ions were accelerated, which resulted in the enrichment of element oxygen and silicon at the spark discharge region. Moreover, due to the compact internal layer, the intensive spark discharge region exhibited more positive potentials with respect to other regions, which meant this region could restrain the ejection of electron and provide effective protection to the substrate. In addition, it was found that oxygen played a vital role in determining the intensity and size of sparks, and abundant oxygen resulted in intensive and larger sparks. (c) 2005 Elsevier B.V. All rights reserved.