Adsorption and electrooxidation of dimethyl ether on platinized platinum electrode in sulfuric acid solution

Adsorption and oxidation of dimethyl ether (DME) on the Pt/Pt electrode from 0.5 M H₂SO₄ is studied by measuring transients of current and potential, charging curves, and curves of electrooxidation in the adsorbed layer and also by cyclic voltammetry and steady-state polarization measurements. The DME adsorption is accompanied by dehydrogenation and destruction of its molecules to form a chemisorbed adsorbate that mainly consists of C1 species (HCO_ads and/or CO_ads) with (under certain conditions) a small amount of species that desorb at cathodic polarization. The adsorption and electrooxidation of DME are inhibited by adsorbed oxygen. The possible schemes of DME oxidation, where the reaction of DME chemisorption products with adsorbed oxygen-containing species is the limiting stage, are discussed.     

Concurrent oxygen reduction and methanol oxidation in sulfuric acid solutions on platinized platinum electrodes

Steady-state polarization curves are compared in solutions of 0.5 M H₂SO₄ + O₂ (saturated), 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH, and 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH + O₂ (saturated) on a Pt/Pt electrode. A considerable difference is found between the currents in mixed solutions and those expected based on the principle of additivity of currents in CH₃OH and O₂ individual solutions. The surface coverages with the CH₃OH and O₂ adsorption products are determined in the potential range of 0.2–0.9 V (RHE). Open-circuit potentials are measured in mixed solutions. The obtained results suggest that the direct heterogeneous interaction between methanol and oxygen occurs alongside with faradaic reactions. This is assumed to lead to a decrease in methanol electrooxidation currents at E ≥ 0.8 V and their increase at E ≤ 0.65 V.     

Rhenium deposition onto platinum surface by reduction of perrhenic acid with methanol in hydrochloric acid media

It has been demonstrated that rhenium deposition onto Pt surface in hydrochloric acid media can also be carried out by reduction of perrhenic acid with methanol. Above 0.5 M Cl⁻ ion concentration, however, it is practical to combine the use of methanol with hydrogen.     

Electrodeposition of rhenium species onto a gold surface in sulfuric acid media

It has been shown that the chemical nature of electrodeposited rhenium species depends on the H₂SO₄ concentration in the supporting electrolyte from which the deposition takes place. In dilute H₂SO₄, mostly ReO₂ and ReO₃ and traces of Re₂O₅ are deposited. With the increase of H₂SO₄ concentration, Re₂O₅ becomes the principal deposit; in H₂SO₄ solution in higher concentration than 10 M, solely Re₂O₅ is deposited. From highly dilute H₂SO₄ solutions (pH0.9), Re⁰ is deposited, which oxidizes at 0.7 V. If the current density of deposition is higher than 80 mA/cm², thermodynamically two types of Re⁰ are deposited and oxidized at 0.7 V and 0.95 V.Presented at the 3rd International Symposium on Electrochemical Processing of Tailored Materials held at the 53rd Annual Meeting of the International Society of Electrochemistry, 15–20 September 2002, Düsseldorf, Germany     

Generation and electrochemical nanogravimetric response of the third anodic hydrogen peak on a platinum electrode in sulfuric acid media

Platinum electrodes have been investigated in sulfuric acid solutions in the hydrogen adsorption–desorption region by electrochemical quartz crystal nanobalance (EQCN). It was found that a well-developed peak (the so-called third peak) between the two main peaks appeared when, following the cycling in the oxide region, the electrode was kept at potentials just more positive than the potential of hydrogen evolution under the same conditions. The extent of this third peak and its ratio to oxidation peaks of the strongly and weakly adsorbed hydrogen depend on the waiting time at potentials mentioned above as well as on the scan rate. Similarly to the other two peaks, the simultaneous EQCN response shows a slight mass increase which can be assigned to adsorption of HSO₄ ^? ions at the platinum surface. Because the third peak appears only after a potential excursion in the oxide region, it is related to the formation of specific surface sites on which hydrogen can be adsorbed with an energy which falls between the energies of the weakly and strongly bound hydrogen. The waiting time effect indicates that this adsorption is a slow process, and it is the very reason that it cannot be observed during the second cycle. The scan rate dependence can be elucidated by the transformation of this type of adsorbed hydrogen to the other two forms.     

Role of adsorption phenomena in the electrocatalytic reduction of nitric acid at a platinized platinum electrode

The electrocatalytic reduction of nitric acid was studied at a platinized platinum electrode in the presence of different supporting electrolytes. It has been found that at low HNO₃ concentrations the polarization behaviour, the shape of the polarization curves and the reduction rate depend significantly upon the supporting electrolyte. (For instance, one maximum in HClO₄, two maxima in H₂SO₄.)With increasing nitric acid concentrations the differences in the character of the polarization curves gradually disappear. The phenomena observed can be explained by the role of competitive adsorption between nitric acid and ions of the supporting electrolyte. Strongly adsorbing chloride ions exert a very pronounced influence on the reduction rate and induce periodical phenomena under certain experimental conditions. The adsorption of chloride ions was studied by a radiotracer method. Results of this study confirm the view on the importance of adsorption competition in the polarization behaviour. On the basis of simple adsorption models an attempt was made to explain the phenomena observed.     

On the electrochemical behaviour of pyruvic and lactic acids at a platinized platinum electrode in acid medium

The electrochemical oxidation of pyruvic and lactic acids at a platinized platinum electrode has been studied in acidic (M H₂SO₄) medium. The oxidation process takes place at potentials more positive than 900–1000 mV (on RHE scale). The final products are acetic acid and CO₂. Unambiguous polarization measurements could be carried out only in the case of preoxidized surfaces. For the interpretation of the phenomena observed, a mechanism involving reactions of organic species with electrochemically formed OH radicals is proposed.Studying the reduction of pyruvic acid, it has been stated that, similar to the behaviour of simple aliphatic ketones, the conversion of the

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group into -CH₂- occurs to a significant extent.     

Electrooxidation and adsorption of oligoelthylene glycols on platinized platinum electrode

The trends in adsorption and oxidation of oligoethylene glycols (OEG), namely, di-, tri-, and tetraethylene glycol, on a Pt/Pt electrode are studied. Using a combination of methods of open-circuit potential shifts at the adsorption of organic species and anodic voltammetric curves, it is established that the OEG adsorption on a Pt/Pt electrode is accompanied by hydrogenation, dehydrogenation, and partial destruction of molecules and also that the amount and composition of accumulated adsorbate depend on the initial adsorption potential and the polymer structure. The OEG oxidation on a platinum electrode is considerably hindered as compared with ethylene glycol. The reaction rate decreases with an increase in the OEG molecular mass and is largely limited by the adsorption of molecules on the electrode surface, which is evidenced by the weak dependence of the rate on the potential in the double layer region.     

Formation and Oxidation of Hydrogen Molybdenum Bronze on Platinum Electrode in Sulfuric Acid Solution

Hydrogen molybdenum bronze (HxMoO3) can be electrodeposited on platinum and oxidized in two steps to the hydrogen molybdenum bronze with less amount of hydrogen HyMoO3 (y相似文献   

Cyclic voltammetry and electrochemical quartz crystal microbalance studies of a rhodized platinum electrode in sulfuric acid solution

The adsorption properties of a rhodized platinum electrode in sulfuric acid were studied through simultaneous cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) measurements. The processes occurring at the Rh surface during the potential scan between 0.04 and 1.3 V were analyzed in terms of the changes in mass and charge. The apparent molar masses of the species adsorbed on Rh in different potential regions were determined from the mass–charge correlation. The results obtained suggest that the desorption of hydrogen UPD initially occurs in conjunction with the incorporation of mass due to the adsorption of bisulfate/sulfate ions between 0.04 V and 0.12 V; the apparent molar mass (M ₁) in this potential region is consistent with that of bisulfate ion, assuming that one sulfate species occupies the site originally occupied by five H atoms. Between 0.12 V and 0.20 V, the apparent molar mass, M ₂, is less than M ₁. This result may be associated with a structural rearrangement of the adsorbed sulfate species. The apparent molar mass, M ₃, was determined in the potential region of 0.20–0.56 V; the value obtained for M ₃ suggests that the adsorbed species are hydrated bisulfate ions (HSO₄⁻·4H₂O). Additionally, it was found that Rh oxides formed at the surface between 0.56 V and 1.3 V could not be directly identified from the correlation between charge and mass.     

Underpotential deposition of cobalt onto polycrystalline platinum

An electrochemical study of cobalt electrodeposition onto a polycrystalline platinum electrode from an aqueous solution (10⁻² M CoCl₂ + 1 M NH₄Cl (pH 9.5)) was carried out through cyclic voltammetry and potential step techniques. Analysis of the voltammetric data clearly showed that a cobalt adlayer is formed during the application of potential in the underpotential deposition (upd) region. Formation of this cobalt adlayer involved the simultaneous presence of both adsorption and 2D nucleation processes. Cobalt adlayers obtained by linear voltammetry in upd region were analyzed employing diffuse reflectance spectroscopy (DRS). By using theoretical quantum studies at PM6//HF/LANL1MB level, it was possible to assign the peaks obtained by DRS at 328 and 337 nm to the cobalt adsorption on Pt(111) and Pt(100), respectively, while the signals recorded at 355 and 362 nm were related with the clean platinum surfaces Pt(100) and Pt(111). Also, quantum calculations at the PM6 level indicated that the energy formation order is Co-Pt(100) > Co-Pt(111) > Co-Pt(110) > Co-Co(surface).     

Initial stages of the copper electrocrystallization from a sulfuric acid electrolyte: Chronoamperometry at a platinum ring-disk electrode

Initial stages of the copper electrocrystallization on platinum from a sulfuric acid electrolyte are studied by measuring potentiostatic current transients (the chronoamperometry method) on a rotating and stationary ring-disk electrode. The number of active centers and the copper nucleation rate are shown to substantially depend on the electrochemical pretreatment of the electrode. The mechanism governing the formation of intermediate species (ions Cu⁺) during the nucleation of a new copper phase and the deposit dissolution is analyzed. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Investigations of copper adsorption in hydrochloric acid media,via the ionization of hydrogen adsorbed on platinized platinum

Copper deposition in hydrochloric acid media, via the ionization of hydrogen adsorbed on platinized platinum, results in an adsorbed metal layer similar to that formed potentiostatically. However, the adsorbed hydrogen is replaced by adsorbed copper only to a certain extent, owing to the formation of Cu⁺ ions. This discrepancy depends on the chloride ion activity and the structure of the platinum black.     

Effect of mass transfer process on hydrogen adsorption on polycrystalline platinum electrode in sulfuric acid solution

The hydrogen adsorption on polycrystalline platinum electrode experimentally as well as on single crystal Pt(110), Pt(100) and Pt(111) electrode theoretically were studied. The study of forced convection on the electrode surface promotes the HUPD research from static process to a convective mode and provides a new strategy to investigate the hydrogen adsorption in solution.     

Role of inhibition by anion adsorption in oscillatory phenomena produced in the course of electrocatalytic reduction of nitric acid at a platinized platinum electrode

Oscillatory phenomena occurring in the course of the reduction of nitric acid at a platinum electrode which were induced by the presence of chloride ions are presented. Both galvanostatic potential oscillations and potentiostatic current oscillations were observed. The influence of different parameters (concentration, current, potential) on the oscillatory behaviour was studied. By use of in situ radiotracer adsorption measurements it has been shown that the periodical changes of electrochemical parameters were coupled with those of chloride ion adsorption.Open-circuit potential oscillations were observed in a hydrogen atmosphere. This observation attests that the external electric circuit does not play a role in the generation of the galvanostatic oscillations.An attempt was made to give an explanation of the phenomena observed under galvanostatic and open-circuit conditions.     

Dynamics of copper deposition from a sulfuric acid solution onto electrically isoconducting electrodes made of fibrous carbon materials

Effect of the initial electrical conductivity of an electrically isoconducting flow-through electrode made of a fibrous carbon material on the dynamics of copper electrodeposition from a sulfuric acid solution was studied. The distribution of the copper deposit across the electrode thickness and the variation of the electrolysis parameters (copper deposition rate, current efficiency, uniformity of distribution, and mass of a deposited metal per unit mass of the fibrous carbon material) were considered.