Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

The chemical nature of P-containing species of varying concentration present in CeO₂ after impregnation with (NH₄)₂HPO₄ and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO₄ (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm⁻²) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO₂ after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm⁻² in all samples. Isolated PO₄ units that could initially be present in the samples calcined at 873 K nucleated and CePO₄ was formed when samples were calcined at 1273 K. OSR properties of CeO₂ deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO₄ at the surface of the P-containing ceria solids.     

Preliminary Investigations On The Reactivity Of Ozone Considering Energy Supplied To Ozone Generators

A simplified engineering analysis developed by investigations of the energy levels and the data of ozone decomposition is presented. Experiments have been conducted by generating ozone from the same ozone generator by two ways and keeping the hydrodynamic conditions identical during ozonation. Ozonation conducted in various media such as gas, gas-liquid and gas-solid supports the assumptions of the presence of excited ozone species and variation in reactivity. The variation in reactivity linked with ozone generation shows an increase in the case of sawdust bleaching. The reactivity is the same for the removal of total organic carbon from water, and a higher ozone decomposition without significant reaction with methyl red solutions and coliform inactivation is observed.     

Molecular dynamics studies of a model polymer-catalyst-carbon interface

Classical molecular dynamics simulations are performed to obtain insights into structural and dynamical behavior of water and O₂ transport through a model polymer membrane, and at the interface of such hydrated polymer with graphite-supported nanocatalyst platinum particles. Water clustering is observed near the membrane hydrophilic sites constituted by sulfonic groups, which due to their affinity with platinum, are located near the metallic surface. It is found that the diffusion of water through the model hydrated polymer membrane depends strongly on the level of membrane hydration due to contribution from various mechanisms whose relative weights change with the degree of hydration. Possible scenarios for O₂ diffusion are also analyzed.     

Belgian Experiences in the Ozonization of Water

After reviewing the uses of ozone in the preparation of drinking water, high purity water for Pharmaceuticals industries, and swimming pools throughout Belgium, a discussion of technological developments made at the Tailfer plant (serving Brussels) concerning the uses of ozone is presented. These subjects include analytical and monitoring techniques developed for ozone, procedures for ozone contacting employed at this plant, treatment of ozone contactor off–gases, and the use of oxygen–enriched process gas to produce supplemental amounts of ozone required periodically. Capital and operating cost data are presented.     

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.