The influence of F doping on the activity of PbO2 film electrodes in oxygen evolution reaction

The PbO₂ and F⁻-doped PbO₂ (F-PbO₂) film electrodes have been prepared by an electrodeposition process onto platinum substrate. The changes of their electrochemical activity for oxygen evolution (OE) reaction with accelerated electrolysis time have been studied. The results show that the activity of the electrodes decreases with increasing electrolysis time. This can be attributed to the conductivity variations, which are caused by the decrease of the oxygen vacancy concentration in PbO₂ films during OE. The mechanism of the decrease of the oxygen vacancies has been investigated. For F-PbO₂ film electrodes, though its electrochemical activity is somewhat lower than that of undoped one, its activity stability is much higher in comparison with that of PbO₂. The influence of F⁻ doping on the activity of PbO₂ film electrodes has been also discussed.     

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

Mass transfer coefficients of styrene and oxygen into silicone oil emulsions in a bubble reactor

The absorption of oxygen and styrene in water-silicone oil emulsions was independently studied in laboratory-scale bubble reactors at a constant gas flow rate for the whole range of emulsion compositions (0-10% v/v). The volumetric mass transfer coefficients to the emulsions were experimentally measured using a dynamic absorption method. It was assumed that the gas phase contacts preferentially the water phase. In the case of oxygen absorption, it was found that the addition of silicone oil hinders oxygen mass transfer compared to an air-water system. Decreases in k_La_oxygen of up to 25% were noted. Such decreases in the oxygen mass transfer coefficient, which imply longer aeration times to transfer oxygen, could represent a limiting step in biotechnological processes strongly dependent on oxygen concentration. Nevertheless, as the large affinity of silicone oil for oxygen enables greater amounts of oxygen to be transferred from the gas phase, it appears that the addition of more than 5% silicone oil should be beneficial to increase the oxygen transfer rate. In the case of styrene absorption, it was established that the volumetric mass transfer coefficient based on the emulsion volume is roughly constant with the increase in the emulsion composition. In spite of the relatively high cost of silicone oil, water-silicone oil emulsions remain relevant to treat low-solubility volatile organic compounds, such as styrene, in low-concentration gas streams.     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

Oxygen reduction activity of Pt and Pt-Mn-Co electrocatalysts sputtered on nano-structured thin film support

We report on extensive measurements of oxygen reduction activity of Pt and Pt-Co-Mn electrocatalysts using the rotating ring-disk electrode (RRDE) method. The electrocatalysts were prepared by sputtering from Pt or Pt, Co and Mn targets onto 3M's nano-structured thin film support (NSTF) structures. The area specific activity of Pt/NSTF, measured in 0.1 M HClO₄ and at room temperature, is similar to that of bulk Pt. The area specific measurements show a 20 mV reduction in the Pt-Co-Mn/NSTF overpotential compared to Pt/NSTF. The corresponding kinetic gain in the area specific activity of the ternary alloy is about a factor of two. This ORR enhancement factor observed in the ternary Pt-Co-Mn/NSTF by RRDE measurements is similar to the results obtained in 50 cm² H₂/air fuel cells.     

OXYGEN TRANSFER IN HORIZONTAL PIPELINE AERATORS WITH NOZZLES

Horizontal pipeline and tubular loop aerators are of interest for fermentation and waste water treatment and are ideally suited for continuous processing. A major drawback is that these pipeline contactors invariably operate in the “elongated bubble and plug” regime in which the mass transfer rate is low. This article evaluates the performance of a horizontal pipeline aerator fitted with nozzles equispaced along its length to enhance mass transfer rates by promoting turbulence and augmenting effective interfacial area. Such devices can also be advantageously used in long pipe lines as in the case of treating waste while it is being transported. Pressure drop and overall liquid-side mass transfer coefficient data are reported as functions of liquid (water) and gas flow rates and nozzle size and spacing. It is shown that for all the conditions studied, k_La = 0.026(ΔP/L)^1.036 and that the pressure gradient is given by a simple correlation, provided an empirical parameter which characterises a nozzle is known. Preliminary investigations on the effect of surfactant ad the presence of suspended solids (size 75 μm) on mass transfer coefficient are also reported. Very high values of power dissipation can be achieved in such aerators without mechanically moving parts and high values of mass transfer coefficient can be realized.     

Role of metal ion impurities in generation of oxygen gas within anodic alumina

The generation of oxygen gas within an amorphous anodic alumina film is reported. The film was formed by anodizing aluminum, which was first electropolished and then chemically polished in CrO₃-H₃PO₄ solution, in sodium tungstate electrolyte. The procedure results in incorporation of mobile Cr³⁺ species, from the chemical polishing film, and mobile W⁶⁺ species, from the electrolyte, into the amorphous structure. The tungsten species are present in the outer 27% of the film thickness, while Cr⁶⁺ species occupy a thin layer within the tungsten-containing region. Above the Cr³⁺ containing layer, a band develops that contains oxygen bubbles of a few nanometres size. The oxygen is generated by oxidation of O²⁻ ions of the alumina. A mechanism of oxygen generation within the alumina is proposed based on the electronic band structure of the oxide, modified by the Cr³⁺ and W⁶⁺ species, and on the ionic transport processes during oxide growth.     

Oxygen evolution anodes composed of anodically deposited Mn-Mo-Fe oxides for seawater electrolysis

Preparation of anodes for oxygen evolution in seawater electrolysis was carried out. Manganese-molybdenum double oxides, Mn_1−xMo_xO_2+x, prepared by anodic deposition from MnSO₄-Na₂MoO₄ solutions showed the 100% oxygen evolution efficiency at a current density of 1000 A m⁻² in 0.5 M NaCl at 30 °C and pH 12, but an increase in solution temperature resulted in dissolution of the oxides as molybdate and permanganate ions. In order to increase the stability of the electrodes at higher temperatures the addition of iron to the manganese-molybdenum oxides was performed by anodic deposition in MnSO₄-Na₂MoO₄-FeNH₄(SO₄)₂ solutions. The electrodes thus prepared showed the 100% oxygen evolution efficiency at 1000 A m⁻² in 0.5 M NaCl at 30-90 °C, when proper amounts of molybdenum and iron were contained. The iron addition also enhanced the oxygen evolution efficiency. The electrodes were not composed of oxide mixtures but triple oxides, Mn_1−x−yMo_xFe_yO_2+x−0.5y, consisting of Mn⁴⁺, Mo⁶⁺ and Fe³⁺. The formation of the triple oxides seemed responsible for enhancement of both oxygen evolution efficiency and stability.     

Oxidation and reforming reactions of CH4 on a stepped Pt(5 5 7) single crystal

The oxidation and reforming kinetics of methane by O₂, CO₂ and H₂O were studied on a stepped Pt(5 5 7) single crystal from 623 to 1050 K under methane rich conditions. The rate of carbon deposition was followed by ex-situ Auger electron spectroscopy under non-oxidative conditions. The apparent activation energy for methane decomposition was significantly lower than the apparent barriers measured for both total oxidation, CO₂ and H₂O reforming. Total oxidation of methane to CO₂ and H₂O followed by combined dry and steam reforming (combined combustion-reforming) led to CO production rates which were higher than direct CO₂ or H₂O reforming rates. The enhanced rates are most likely due to the ability of adsorbed oxygen to prevent carbon nucleation and/or scavenge carbon enabling the reforming reaction to turnover on a larger fraction of sites. Comparable amounts of carbon were found by Auger electron spectroscopy measurements after both direct dry or steam reforming, while combined oxidation-reforming had considerable less carbon. During direct dry or steam reforming, CO₂ and H₂O serve only to scavenge adsorbed atomic carbon, while in the presence of oxygen, carbon is removed by both combustion and reforming routes.