Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.

A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex

Liquid-phase homogeneous catalytic oxidation of styrene with Wilkinson complex by molecular oxygen in toluene medium gave selectively benzaldehyde and formaldehyde as the primary products. Higher temperatures and styrene conversions eventually led to acid formation due to co-oxidation of aldehyde.A reaction induction period and an initiation period, typical of free-radical reactions, characterized the oxidation process. The effects of temperature and catalyst and styrene concentrations on the conversion of styrene to benzaldehyde and acid formation have been studied. The optimum reaction parameters have been determined as a styrene-to-solvent mole ratio of 0.5, a catalyst-to-styrene mole ratio of 5.0 X lo4, and a reaction temperature of 75 "C. A reaction scheme based upon free-radical mechanism yielded a pseudo-first-order model which agreed well with the observed kinetic data in the absence of co-oxidation of aldehyde. A second-order model was found to fit the experimental data better in the case of aldehyde conversion to acid.

Role of lattice defects and crystallite morphology in the UV and visible-light-induced photo-catalytic properties of combustion-prepared TiO2

The physico-chemical, photo-physical and micro-structural properties responsible for the strikingly different photocatalytic behavior of combustion-prepared TiO2 (c.TiO2) and Degussa P25 (d.TiO2) samples are elucidated in this study. Electron microscopy and selected area electron diffraction micrographs revealed that the two samples exhibited different morphologies. The grains of c.TiO2 were spherical and comprised of 5-6 nm size primary particle. On the other hand, d.TiO2 consisted of large (0.5-3.0 mu m) size and irregular shape aggregates having primary particles of 15-40 nm cross-sectional diameter. The ESR study revealed that the presence of certain defect states in c.TiO2 helped in stabilization of O-. and Ti3+-OH type species during room-temperature UV-irradiation. No such paramagnetic species were however formed over d.TiO2 under similar conditions. C1s and Ti 2p XPS spectra provide evidence for the presence of some lattice vacancies in c.TiO2 and also for the bulk Ti4+ -> Ti3+ conversion during its UV-irradiation. Compared to d.TiO2, c.TiO2 displayed considerably higher activity for discoloration of methyl orange but very poor activity for splitting of water, both under UV and visible light radiations. This is attributed to enhanced surface adsorption of dye molecules over c.TiO2, because of its textural features and also the presence of photo-active ion-radicals. On the other hand, the poor activity of c.TiO2 for water splitting is related to certain defect-induced inter-band charge trapping states in the close vicinity of valence and conduction bands of c.TiO2, as revealed by thermoluminescence spectroscopy. Further, the dispersion of nanosize gold particles gave rise to augmented activity of both the catalysts, particularly for water splitting. This is explained by the promotional role of Au-0 or Au-0/TiO2 interfacial sites in the adsorption and charge-adsorbate interaction processes. (C) 2011 Elsevier B.V. All rights reserved.

Kinetic study on the photo-catalytic degradation of pyridine in TiO2 suspension systems

It has been generally agreed that pyridine can be effectively mineralized in aerated TiO2 slurries using near-UV irradiation. The knowledge on the kinetics of the system possesses both practical and theoretical values. The present study, on the base of Langmuir-Hinshewood mechanism, illustrates a pseudo first-order kinetic model of the degradation with the limiting rate constant of 3.004 mg l(-1) min(-1) and equilibrium adsorption constant 2.763 x 10(-2) l mg(-1), respectively. The degradation efficiency in alkali is a little higher than that in acid with a minimum at about pH = 5, which is explained by the formation of acid-pyridine in acidic surrounding together with the amphoteric nature of the TiO2 surface. The promotion of H2O2 on the photo-degradation ties in its supplying proper amount of (OH)-O-. radicals for the inducement stage before surface redox reactions. (C) 2004 Elsevier B.V. All rights reserved.

Photo-sensitized oxidation in natural water via .OH radicals

A method is presented for determining production and consumption rates of .OH radicals produced photochemically in natural surface waters. It is based on the determination of the kinetics by which the concentration of a specified trace compound decreases during irradiation. In samples from Lake Greifensee (Switzerland) low production rates for .OH limit its possible effects. In addition, fast consumptions by the natural dissolved organic solutes and by the bicarbonate protect organic micropollutants from oxidation by .OH. Neither direct nor indirect H2O2 photolysis was a significant source of .OH in the lakewater studied lacking iron, whereas nitrate photolysis could have been a source. Comparison with reaction kinetic formulations allows generalizations for other types of waters.

Catalytic oxidation of cyclohexane over Ti-Zr-Co catalysts

Ti-Zr-Co alloys have been fabricated and characterized, and their catalytic performance was discussed for the oxidation of cyclohexane with oxygen under solvent-free condition. The icosahedral quasicrystalline phase (I-phase)-forming ability of Ti-Zr-Co alloys with different compositions was discussed, and it was confirmed that I-phase could be formed as a dominating phase at the Ti-rich composition region from Ti53Zr27Co20 to Ti75Zr5Co20 in as-cast alloys. The composition and microstructure of Ti-Zr-Co alloys present crucial influences on its catalytic activity and selectivity in the oxidation of cyclohexane. The influences of some reaction parameters such as temperature, reaction time, and catalyst amounts were also investigated. Ti70Zr10Co20 alloy containing quasicrystal microstructure showed good catalytic performance with a 6.8% conversion of cyclohexane and 90.4% selectivity of cyclohexanol and cyclohexanone. It behaves as an efficient heterogeneous catalyst for the oxidation of cyclohexane and could be recycled five times without loss in activity and selectivity.

Catalytic oxidation of cyclohexene to cyclohexanone by a triple system in acidic aqueous acetonitrile medium

The catalytic oxidation of cyclohexene to cyclohexanone using Pd(OAc)(2)/HQ/FePc was investigated in an acidic aqueous solution of acetonitrile. The role of each component of this system in the oxidation of cyclohexene was explored by means of UV-VIS, IR, XPS spectroscopy and. cyclic voltammetry, respectively. Based on the experimental results, the mechanism of the oxidation of cyclohexene catalyzed by Pd(OAc)(2)/HQ/FePc was elucidated.