Corrosion process of stainless steel in natural brine as a source of chromium and iron - the need for routine analysis.

The corrosion of the installations carrying high salinity water is particularly important in the case of utility and therapeutic waters, such as natural brine. The analysis of such complex systems is challenging in the context of routine analysis of Fe and Cr. Both elements can be determined by UV-Vis spectrophotometry after only 1 : 100 dilution and liquid-liquid extraction (LODFe = 0.03 mg L-1) or thermal chloride stripping (LODCr = 0.02 mg L-1). The corrosion process was characterized. Electrochemically accelerated corrosion showed uneven decomposition of the steel components - Cr is less easily released to the solution than Fe. Iron comprises 53% of the dissolved part, and Cr comprises 8.6%, while the steel originally contained 62% of Fe and 18% of Cr. During the short-term (one week) contact of the brine with stainless steel, the amounts of Fe and Cr released to the brine were insignificant from the perspective of its therapeutic value.

The Effect of an External Magnetic Field on the Electrocatalytic Activity of Heat-Treated Cyanometallate Complexes towards the Oxygen Reduction Reaction in an Alkaline Medium.

This work focuses on the development of an electrocatalytic material by annealing a composite of a transition metal coordination material, iron hexacyanoferrate (Prussian blue) immobilized on carboxylic-acid-functionalized reduced graphene oxide. Pyrolysis at 500 °C under a nitrogen atmosphere formed nanoporous core-shell structures with efficient activity, which mostly included iron carbide species capable of participating in the oxygen reduction reaction in alkaline media. The physicochemical properties of the iron-based catalyst were elucidated using transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, and various electrochemical techniques, such as cyclic voltammetry and rotating ring-disk electrode (RRDE) voltammetry. To improve the electroreduction of oxygen over the studied catalytic material, an external magnetic field was utilized, which positively shifted the potential by ca. 20 mV. The formation of undesirable intermediate peroxide species was decreased compared with the ORR measurements without an external magnetic field.

The Influence of the Type of Electrolyte in the Modifying Solution on the Protective Properties of Vinyltrimethoysilane/Ethanol-Based Coatings Formed on Stainless Steel X20Cr13.

The paper reports the results of the examination of the protective properties of silane coatings based on vinyltrimethoxysilane (VTMS) and ethanol (EtOH), doped with the following electrolytes: acetic acid (AcOH), lithium perchlorate LiClO4, sulphuric acid (VI) H2SO4 and ammonia NH3. The coatings were deposited on stainless steel X20Cr13 by the sol-gel dip-coating method. The obtained VTMS/EtOH/Electrolyte coatings were characterized in terms of corrosion resistance, surface morphology and adhesion to the steel substrate. Corrosion tests were conducted in sulphate media acidified up to pH = 2 with and without chloride ions Cl-, respectively. The effectiveness of corrosion protection was determined using potentiometric curves. It has been demonstrated that the coatings under study slow down the processes of corrosion of the steel substrate, thus effectively protecting it against corrosion.

Simplification of organic matter before voltammetric determination of Tl(I) and Tl(III) in water using nanostructured photocatalyst and solar light.

The crucial point of this study was to verify the hypothesis that both thallium species are not affected by the procedure of photolysis when it is applied as a method of simplification of sample matrix containing surfactants, and that this method of sample pretreatment leads to reliable results of Tl speciation analysis. It is important especially because of high instability of Tl(III), which makes partial reduction of Tl(III)DTPA complex unavoidable. After conservation of Tl speciation by addition of DTPA the photolysis assisted with nanostructured hierarchically organized film was performed using "solar lamp" (Fe2O3/WO3/Fe2O3 film, pH 6, 380-800 nm). The results imply that under proposed photolysis conditions Tl(I) is not oxidized in the presence of water matrix, SDS nor DTPA. Also, even 100-fold excess of Fe(III) ions over Tl(I) ions does not accelerate the oxidation of Tl(I) to Tl(III), and already 2 h of heterogeneous photolysis allow to limit the interferences caused by SDS and obtain reliable results. The data obtained by anodic stripping voltammetry (ASV) were verified using an inter-method comparison with SEC ICP MS. Moreover, after 2 h irradiation the reduction rate of Tl(III)DTPA standard solution increased only slightly from 2-3% to 4-6%. The presence of river water matrix causes a slightly higher (9%) reduction of the trivalent form. These changes are irrelevant in the context of instability of Tl(III) compounds. This study indicates that "soft decomposition" can be applied in speciation analysis of thallium in water matrix.

Organic matter decomposition before arsenic speciation analysis of water sample - "Soft decomposition" using nano-photocatalysts.

The applicability of photolysis in the speciation analysis of arsenic is investigated. The use of nano scale semiconductors (Fe2O3/WO3/Fe2O3 at pH 6) as an active film during solar light irradiation of a water sample, containing some surfactants (SDS), results in the simplification of the organic matter and gives no speciation change in the arsenic. The reproducibility of active layer is shown to be high and the surface roughness of each photoactive sample and photocurrent do not differ by more than 6 and less than 8%, respectively. The procedure of sample pretreatment caused a minimum (8-10%) amount of speciation change, whilst the irradiation is no longer that 2 h. The study indicates that "soft decomposition" can be performed for as long as 4 h, and still give photostable arsenates (III) and methylarsenate species. However, the saturation of the water sample with Ar is required (to reduce the oxygen content) for the longer the decomposition time being applied.

Amperometric detector for gas chromatography based on a silica sol-gel solid electrolyte.

An electrochemical cell comprising a silica sol-gel solid electrolyte, a working electrode that protrudes into a gas phase, and reference and counter electrodes that contact the solid electrolyte comprises an amperometric detector for gas chromatography. Under potentiostatic conditions, a current related to the concentration of an analyte in the gas phase is produced by its oxidation at the three-phase boundary among the sol-gel, working electrode, and the gas phase. The sol-gel is processed to contain an electrolyte that also serves as a humidistat to maintain a constant water activity even in the presence the gas chromatographic mobile phase. Response was demonstrated toward a diverse set of analytes, namely hydrogen, 1,2-ethandithiol, phenol, p-cresol, and thioanisole. Using flow injection amperometry of hydrogen with He as the carrier gas, 90% of the steady-state current was achieved in < 1s at a flow rate of 20mLmin-1. A separation of 1,2-ethandithiol, phenol, p-cresol, and thioanisole at a 2.2mLmin-1 flow rate was achieved with respective detection limits (k = 3 criterion) of 4, 1, 3, and 70 ppmv when the working electrode potential was 800mV.

PtIr-WO3 nanostructured alloy for electrocatalytic oxidation of ethylene glycol and ethanol.

In this article, we characterized tungsten oxide-decorated carbon-supported PtIr nanoparticles and tested it for the electrooxidation reactions of ethylene glycol and ethanol. Phase and morphological evaluation of the proposed electrocatalytic materials are investigated employing various characterization techniques including X-ray diffraction (XRD) and transmission electron microscopy (TEM). Electrochemical diagnostic measurements such as cyclic voltammetry, chronoamperometry, and linear sweep voltammetry revealed that the tungsten oxide-modified PtIr/Vulcan nanoparticles have higher catalytic activity for ethylene glycol and ethanol electrooxidation than that of PtIr/Vulcan. A significant enhancement for electrooxidation of CO-adsorbate monolayers occurred in the presence of a transition metal oxide relative to that of pure PtIr/Vulcan electrocatalyst. The likely reasons for this are modification on the Pt center electronic structure and/or increasing the population of reactive oxo groups at the PtIr/Vulcan electrocatalytic interface in different potential regions.

ABTS-modified multiwalled carbon nanotubes as an effective mediating system for bioelectrocatalytic reduction of oxygen.

The ability of such a common redox mediator as 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) to undergo sorption on carbon surfaces is explored here to convert multiwalled carbon nanotubes (CNTs) into a stable colloidal solution of ABTS-modified carbon nanostructures, the diameters of which are approximately 10 nm (as determined by transmission electron microscopy). Subsequently, inks composed of fungal laccase (Cerrena unicolor) mixed with the dispersion of ABTS-modified CNTs and stabilized with Nafion, were deposited on glassy carbon and successfully employed to the reduction of oxygen in McIlvain buffer at pH 5.2. For comparison, the systems utilizing only ABTS-free CNTs and laccase as well as ABTS-modified CNTs did not show appreciable activity toward the oxygen reduction. The three-dimensionally distributed ABTS-modified CNTs are expected to improve the film's overall conductivity and to facilitate electrical connection between the electrode and the enzyme. The network film of ABTS-modified CNTs is rigid, and it is characterized by charge propagation capabilities comparable to the conventional redox polymers. The whole concept of utilization of CNTs modified with ultrathin films of redox mediators in the preparation of efficient bioelectrocatalytic films seems to be of general importance to electroanalytical chemistry and to the development of biosensors.

Hybrid bioelectrocatalyst for hydrogen peroxide reduction: immobilization of enzyme within organic-inorganic film of structured Prussian Blue and PEDOT.

Fabrication of structured film (on glassy carbon substrate) composed of compact Prussian Blue (that has been prepared by alternate immersions and through assembling within ultra-thin layers of 4(pyrrole-1-yl)-benzoic acid, PPyBA) and poly(3,4-ethylendioxythiophene), PEDOT, is described. This functionalized film has been characterized by fast charge propagation, and it has served as a redox conducting template for permanent attachment of a model enzyme, horseradish peroxidase, HRP. The resulting organic-inorganic system acts as an effective hybrid bioelectrocatalyst for electroreduction of hydrogen peroxide, a model reactant for biosensors and biofuel cells. Among important issues are rigidity, permanence of enzyme attachment, morphology, hydrophilicity, and attractive mediating capabilities of the PEDOT-stabilized Prussian Blue based structured film.

Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles.

We develop a concept of fabrication of the multilayer network films on electrodes by exploring the ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo(12)O(40)(3-)), to form stable anionic monolayers (templates) on carbon and metals including platinum. By repeated alternate treatments in the solution of PMo(12)O(40)(3-) (or in the colloidal suspension of polyoxometallate-protected Pt-nanoparticles) and in the solution of monomer (e.g. anilinium) cations, the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional assemblies on electrode (e.g. glassy carbon) surfaces. In the resulting hybrid (organic-inorganic) films, the layers of negatively charged polyoxometallate, or polyoxometallate-protected (stabilized) Pt-nanoparticles, are linked or electrostatically attracted by ultra-thin layers of such positively charged conducting polymers as polyaniline (PANI), polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene), PEDOT. Consequently, the attractive physicochemical properties of polymers and reactivity of polyoxometallate or noble metal particles are combined. The films are functionalized and show electrocatalytic properties towards reduction of nitrite, bromate, hydrogen peroxide or oxygen. They are of importance to the chemical and biochemical sensing as well as to the biochemical and medical applications.

Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.