4-Benzoylbenzoate intercalated in layered double hydroxides: a new catalyst for photo-oxidation of sulfides in solution and in the gas phase

A new mixed organic-inorganic photosensitizer, based on 4-benzoylbenzoate intercalated into a layered double hydroxide has been prepared, characterized and successfully tested for the photo-oxidation of dialkylsulfides, both in acetonitrile and in the gas phase.     

Photooxidation of aqueous trichloroethylene using a buoyant photocatalyst with reaction progress monitored via micro-headspace GC/MS

Although photooxidation has previously been shown to be successful in removing organic contaminants from water, methods combining the rapid photooxidation of the desired contaminant with easy catalyst manipulation and removal are few and far between. In the absence of an easy means of catalyst removal, the photooxidation process becomes more costly and time consuming, and photocatalysis cannot be employed as an in situ method for the remediation of aqueous organic contaminants. In this study, the photocatalyst was added to an aqueous trichloroethylene (TCE) solution in the form of TiO₂-coated buoyant microspheres. The solution, placed in a flow-cell photoreactor along with the buoyant catalyst, was irradiated with a UV-filtered Xenon light source. Limited sample sizes necessitated the development of a low-cost headspace GC/MS analysis method, utilizing a standard direct-injection autosampler. This analytical technique aptly monitored reaction progress and indicated that aqueous TCE concentration decreases by nearly 90% in the first hour of irradiation. Subsequent solvent extraction GC/MS analysis indicated that the TCE is initially sorbed by the photocatalyst spheres, but as irradiation continued, TCE is removed from the catalyst spheres surfaces. During the course of irradiation, the expected TCE mineralization product hydrochloric acid appeared, as indicated by a decrease in pH and ion chromatography analysis. The microsphere-born catalyst was easily removed from the treated solution by filtration. Thus, it is possible that a method for effective, low-cost in situ photooxidation of aqueous organic contaminants will be realized in the near future.     

Photooxidation of aryl alkanes by a decatungstate/triethylsilane system in the presence of molecular oxygen

Decatungstate photocatalyzes the oxidation of aryl alkanes to the corresponding tertiary hydroperoxides and alcohols, in the presence of molecular oxygen. The addition of triethylsilane to the reaction mixture substantially increases the proportion of hydroperoxide formed.     

红外光谱法研究含CeSt3的LDPE膜紫外光氧降解

报道了硬脂酸铈（ＣｅＳｔ_３）、及其在各种浓度、或不同温度、或延长贮放时间下含ＣｅＳｔ_３的低密度聚乙烯（ＬＤＰＥ）膜紫外光氧化降解过程的红外光谱。结果表明，只要在ＬＤＰＥ膜中加入０．１ｗｔ＋％～０．３ｗｔ＋％ＣｅＳｔ_３光敏剂，即可控光降解ＬＤＰＥ膜的寿命。     

Influence of nanodispersed boehmite on polypropylene photooxidation

Nanocomposites containing pure or organically modified nanoboehmites of different sizes were prepared by melt compounding with polypropylene. The samples were UV light irradiated in artificial accelerated conditions representative of solar irradiation (λ > 300 nm) at 60 °C in air. The chemical modifications resulting from photooxidation were followed by IR and UV-visible spectroscopies. The presence of pristine nanoboehmites was shown to change the rate of oxidation of polypropylene by reducing the oxidation induction period due to the presence of residual processing antioxidant. The differences of the oxidation induction periods between the nanocomposites and the pristine polymer disappear after solvent extraction of the antioxidant. The inefficiency of traditional antioxidant in retarding the photooxidation of polypropylene containing nanodispersed boehmite is proved. Antioxidant migration to the boehmite surface induced by the preferential interaction with the polar filler is proposed as an explanation. The oxidative behaviour of the organically modified boehmites was shown to depend on the type of organic substituent. p-Toluenesulfonate reduces the adsorption of antioxidants while the presence of a long-chain alkyl benzensulfonate increased the oxidation rate by generation of radical initiators.     

Photodegradation of polypropylene thermal bonded non-woven fabric

Samples of thermal bonded polypropylene non-woven fabrics were exposed to light from two TUV 30W G30T8 Philips lamps (λ = 253.7 nm) in a covered open-air chamber at room temperature (25 °C and 55% relative humidity) for different periods of time. In order to determine the state of degradation, the samples were examined by optical microscopy, scanning electron microscopy, staining with an isopropanol solution of methylene blue and Sudan III, colourimetry, Fourier transform infrared (FTIR) spectroscopy and density measurements. Although the bonded areas formed under complex thermal and mechanical deformations during the fabric production, no localized staining was observed. The colour of the irradiated and stained fabrics changed uniformly due to the even production of polar groups in the process of irradiation. It was found that the change of redness and blueness of degraded and stained samples can be correlated linearly with the evolution of POOH groups as determined by FTIR spectroscopy. Products containing carbonyl (CO), hydroxyl and/or hydroperoxide (POOH) groups increase with time of degradation with a non-linear relation. It was also observed that the density and 997 cm⁻¹/972 cm⁻¹ FTIR absorbance ratio increases with degradation time. Density fluctuation and the build up of degradation products caused fibre cracks and embrittlement.     

Preparation and characterization of high-specific-surface-area activated carbons from K2CO3-treated waste polyurethane

An activated carbon with high specific surface area was prepared from polyurethane foam by chemical activation with K2CO3 and the influences of carbonization temperature and impregnation ratio on the pore structure of the prepared activated carbon were investigated. It was found that the specific surface area of the activated carbon was at a maximum value (about 2800 m(2)/g) at a carbonization temperature of 1073 K and at an impregnation ratio of 1.0. It was concluded that the polyurethane foam structure was modified during impregnation by K2CO3, K2CO3 promoted charring during carbonization, and then the weight loss behavior was changed below 700 and above 1000 K, carbon in the char was consumed by K2CO3 reduction, and this led to the high specific surface area. The prepared activated carbon had a very sharp micropore size distribution, compared with the commercial activated carbon having high specific surface area. The amounts of three organic vapors (benzene, acetone, and octane) adsorbed on the prepared activated carbons was much larger than those on the traditional coconut shell AC and the same as those on the commercial activated carbon except for octane. We surmised that the high specific surface area was due to the modification of the carbonization behavior of polyurethane foam by K2CO3.     

Photooxidation of Selected Polycyclic Aromatic Hydrocarbons in Aqueous Organic Media in The Presence of Ti(IV)Oxide

Abstract

We have studied the photooxidation of selected polycyclic aromatic hydrocarbons (PAH) in the presence of Ti(IV)oxide in a mixed solvent system consisting of N-methylpyrrolidinone (NMP) and water. Reaction rates for the photooxidation of acenaphthylene and pyrene were investigated by monitoring the disappearance of the PAH substrate from the reaction mixture as a function of time. For both compounds plots of In C_o/C_t, as a function of time yielded straight lines, indicating first order kinetics with respect to the substrate. With an initial acenaphthylene concentration of 1.0 gL^?1 the first order reaction rate constant was 0.19 hr^?1 and the half life was 3.7 hr. With an initial pyrene concentration of 0.2 gL^?1 the first order reaction rate constant was 0.0285 hr^?1 and the half life was 24 hr. The photoproducts were characterized by high performance liquid chromatography with diode-array detection (HPLC/DAD) and by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (APCI/LC-MS). Although a number of simple oxidation products were identified the bulk of the photoproducts consisted of the parent PAH substituted with one or more solvent (NMP) molecules. The product mixtures from the photooxidation of the non-mutagens acenaphthylene and pyrene were found to be also non-mutagenic in our Salmonella typhimurium forward mutation assay.     

Photo- and thermal-oxidation of polyethylene: Comparison of mechanisms and influence of unsaturation content

The behaviour of polyethylene with different contents in vinyl and t-vinylene groups have been studied by photooxidation with λ ≥ 300 nm light or by thermooxidation at a temperature of 100 °C. The oxidation was studied by infrared spectroscopy and it was shown that the same oxidation products were obtained, but with different relative concentrations depending on the conditions of ageing, i.e. photochemical or thermal conditions. The mechanisms by which the oxidation products are formed were recalled. The differences between photo- and thermo-oxidation were evidenced on the basis of the stability of ketones that do not accumulate in photochemical conditions, as a result of Norrish reactions. The influence of the initial amount of unsaturated groups on the rates of oxidation was characterized. It was shown that the concentration of unsaturations had no effect on the rate of photooxidation but dramatically influenced the stability in thermooxidative conditions.     

(Co)oxidation/cyclization processes upon irradiation of triphenylamine

Irradiation of triphenylamine (Ph₃N) in nitrogen-flushed solution leads to 9-phenylcarbazole and two tetrahydroderivatives (1,2,3,4- and 1,2,7,8-) via disproportionation of the corresponding 4a,4b-dihydrocarbazole. In oxygen-equilibrated solution oxidative cyclization occurs through the intermediacy of a triplet peroxy diradical, which either abstracts a hydrogen atom intramolecularly or (mainly) cleaves back to the reagents. The role of the key intermediates is supported by DFT calculations and by trapping by triarylphosphines (that are thus efficiently oxidized, while preventing the cyclization of Ph₃N). The hydroperoxide, on the other hand, causes inefficient co-oxidation of sulfides.