Kinetics and Mechanism of the Photo-oxidation of Thiophene by O_2 Adsorbed on Molecular Sieves

Photochemical oxidation of thiophene in n-octane/water extraction system using O2 as oxidant was studied. The reaction mechanism ofthiophene oxidation was proposed. Results obtained here can be used as the reference for the oxidative desulfurization of gasoline because thiophene is one of the main components containing sulfur in fluid catalytic cracking gasoline. Thiophene dissolved in n-octane was photodecomposed and removed into the water phase at ambient temperature and atmospheric pressure. A 500 W high-pressure mercury lamp （main wave length 365 nm, 0.22 kW/m） was used as light source for irradiation, and air was introduced by a gas pump to supply O2. Thiophene can be photo-oxidized to sulfone, oxalic acid, SO4^2-, and CO2. The desulfurization yield of thiophene in n-octane is 58.9% under photo-irradiation for 5 h under the conditions of air flow at 150 mL/min and V（water）：V（n-octane）=1：1. It can be improved to 92.3% by adding 0.15 g zeoliteartificial into 100 mL reaction system, which is the adsorbent for O2 and thiophene. And under such conditions, the photo-oxidation kinetics of thiophene with O2/zeoliteartificial is first-order with an apparent rate constant of 0.5047 h^-1 and a half-time of 1.37 h. The sulfur content can be depressed from 800 μL/L to less than 62 μL/L.

Enhanced visible-light photo-oxidation of nitric oxide using bismuth-coupled graphitic carbon nitride composite heterostructures

Pure bismuth（Bi） metal-modified graphitic carbon nitride（g-C3N4） composites（Bi-CN） with a pomegranate-like structure were prepared by an in situ method.The Bi-CN composites were used as photocatalysts for the oxidation of nitric oxide（NO） under visible-light irradiation.The inclusion of pure Bi metal in the g-C3N4 layers markedly improved the light absorption of the Bi-CN composites from the ultraviolet to the near-infrared region because of the typical surface plasmon resonance of Bi metal.The separation and transfer of photogenerated charge carriers were greatly accelerated by the presence of built-in Mott-Schottky effects at the interface between Bi metal and g-C3N4.As a result,the Bi-CN composite photocatalysts exhibited considerably enhanced efficiency in the photocatalytic removal of NO compared with that of Bi metal or g-C3N4 alone.The pomegranate-like structure of the Bi-CN composites and an explanation for their improved photocatalytic activity were proposed.This work not only provides a design for highly efficient g-C3N4-based photocatalysts through modification with Bi metal,but also offers new insights into the mechanistic understanding of g-C3N4-based photo catalysis.

EFFECTS OF ORGANIC COLORANTS ON PHOTO-INITIATED CROSSLINKING AND PHOTO-OXIDATION DEGRADATION OF POLYETHYLENE AND RELATED MECHANISM

The effects of three organic colorants on photo-initiated crosslinking and photo-oxidation degradation of polyethylene (PE) samples irradiated by microwave excited (MWE) UV lamp in the melt and the related mechanism have been studied by gel content and thermal extension rate determinations,X-ray photoelectron spectroscopy (XPS),mechanical property tests,UV spectroscopy,and light microscope.The data from the gel content and thermal extension rate determinations of photo-crosslinked polyethylene (XLPE) sample...

Synergetic effects of photo-oxidation and biodegradation on failure behavior of polyester coating in tropical rain forest atmosphere

This work aimed to study the comprehensive effects of photo-oxidation and biodegradation on different failure stages of polyester coatings,which were exposed to the tropical rainforest atmosphere.The surface morphology,aging products,local aging characteristics and electrochemical behavior of the coatings were characterized with scanning electron microscope(SEM),fourier transform infrared spectroscopy(FTIR),electrochemical impedance spectroscopy(EIS)and high-resolution dispersive Raman microscope.The results showed that the surface of coatings became rougher and fungal hyphae distributed more densely on surface with the increasing of exposure time.From the aspect of polymer structure,the ultraviolet radiation destroyed the main chain of polyester through the photo-oxidation process,resulting in the breakage of aliphatic ester bonds and the formation of esters.Further,the metabolites of fungi can promote the hydrolysis of oligomers produced by the photo-oxidation.In a short,the photo-oxidation could facilitate the biodegradation of the coating.With the synergistic effect of UV photo-oxidation and fungal biodegradation,a rapid diffusion tunnel between the coating surface and the metal substrate was established at the pore defects of the coating,which finally accelerated the corrosion failure process of the coating.The main corrosion products includeα-Fe_(2)O_(3),ZnO and Zn_(5)(OH)_(6)(CO_(3))_(2).

Infectious Behavior in Photo-oxidation of Polymers

When a polymer is used together with others,its aging process will be affected by the adjacent polymers.This infectious behavior between polymers makes the aging process more complex than that of an individual material.In this study,infectious behavior in photooxidation of polymers was investigated.Polypropylenes(PPs),an unstabilized PP and a commercial PP,were chosen as the infection sources.Six typical polymers,high density polyethylene(HDPE),low density polyethylene(LDPE),polystyrene(PS),polycarbonate(PC),poly(ethylene terephthalate)(PET),and polyamide 6(PA6),were used as the targets.The degree of oxidation of the targets was evaluated by attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR).An accelerating effect of two infection sources on the photo-oxidation of the target polymers was observed.Potential infectious agents from the infection sources were detected by pyrolysis-gas chromatography-mass spectrometry(Py-GC-MS)and gas chromatography(GC).The acceleration effect of two main infectious agents,i.e.acetone and acetic acid,on the photo-oxidation of the commercial PP was verified.The infectious effect of the infection source on the target polymer was considered to be a comprehensive result of the effects of a variety of infectious agents.

SiO2-coated pure anatase TiO2 catalysts for enhanced photo-oxidation of naphthalene and anthracene

Our current efforts reveal the preparation of SiO2@TiO2 nanocomposites having different thicknesses of silica shell and the relationship to photocatalytic activity （PCA） for the photo-oxidation of naph-thalene and anthracene. The presence of SiO2 coating over TiO2 surface was demonstrated by FT-IR analysis, with peaks corresponding to Si-O-Si （1081 cm 1） and Si-O-Ti （950 cm-1） bonds observed. High-resolution transmission electron microscopy analysis confirmed the presence of SiO2 in the as- prepared nanocomposites and the amount of Si, Ti, and O was determined by energy dispersive X-ray spectroscopy analysis. Increasing the Si02 shell thickness increases the surface area of the nanocompos- ites （69-235 m2/g）, which enhances naphthalene/anthracene adsorption. However, the observed PCA trend presents an inverse correlation to the adsorption studies, where the as-prepared samples possess- ing the highest surface areas exhibited the least PCA, while catalysts having lower surface areas （among silica coated samples） displayed the highest PCA in the degradation of naphthalene and anthracene to CO2. Despite complete degradation of naphthalene and anthracene, incomplete mineralization occurred, ascribed to the formation of various intermediates, identified by GC-MS analysis.

Accelerating Role of Clay in Photo-Oxidation of Polypropylene/Clay Multifilament Yarns

Photo-oxidative degradation of polypropylene/clay multifilament yarns containing different amounts of clay was investigated. These samples and pure polypropylene （PP） multifilametns were exposed to long wavelength radiations （λ〉 300 nm） under atmospheric condition of constant temperature and relative humidity. The photo-oxidative stability was studied using FTIR spectroscopy, tensile testing and microscopy. The results indicate that the addition of clay particles decreases the stability of PP/clay composites to photo-oxidative degradation according to comparison with pure PP. From FTIR study and tensile properties, it was also found that the multifilaments with higher clay loading reveals a faster loss of mechanical properties, higher photo-oxidative product formation and more reduction in the induction time of photo-oxidation. Moreover, the crack formation on surface of irradiated filaments corresponds well to the conclusions in tensile properties and FTIR characterization.

Dye-sensitized photo-oxidation of disulfiram

Dye-sensitized photo-oxidation of disulfiram has been carried out under various reaction conditions including change in solvents and sensitizers. The product has been isolated and characterized by its physical, chemical and spectral data. To confirm the participation of singlet-oxygen in the reaction, the experiment has also been carried out in the presence of various singlet oxygen scavengers.

Experimental model of photo-oxidative damage

Background:Retinal degeneration is a common feature of several retinal diseases,such as retinitis pigmentosa and age-related macular degeneration(AMD).In this respect,experimental models of photo-oxidative damage reproduce faithfully photoreceptor loss and many pathophysiological events involved in the activation of retinal cell degeneration.Therefore,such models represent a useful tool to study the mechanisms related to cell death.Their advantage consists in the possibility of modulating the severity of damage according to the needs of the experimenter.Indeed,bright light exposure could be regulated in both time and intensity to trigger a burst of apoptosis in photoreceptors,allowing the study of degenerative mechanisms in a controlled fashion,compared to the progressive and slower rate of death in other genetic models of photoreceptor degeneration.Methods:Here,an exemplificative protocol of bright light exposure in albino rat is described,as well as the main outcomes in retinal function,photoreceptor death,oxidative stress,and inflammation,which characterize this model and reproduce the main features of retinal degeneration diseases.Discussion:Models of photo-oxidative damage represent a useful tool to study the mechanisms responsible for photoreceptor degeneration.In this respect,it is important to adapt the exposure paradigm to the experimental needs,and the wide range of variables and limitations influencing the final outcomes should be considered to achieve proper results.Trial Registration:None.

PHOTOCHEMICAL OXIDATION OF BENZOTHIOPHENE IN SEAWATER

Kinetic investigation into the phogochemical oxidation of benzothiophene in seawater showed that photo-oxidation rates of benzothiophene were influenced by the medium,pH,heary metal ion,dissolved oxygen,and light intensity.The photo-oxidation of benzothiophene followed the first order reaction law, with the rate constants ranging from 1.21×10 -5 /s to 5.38×10 -5 /s.An interesting observation was that the presence of Hg 2+ could markedly enhance the photo-oxidation rate of benzothiophene in seawater;and that the photo-oxidation rate of benzothiophene increased with light intensity.The effect of oxygen on the rate constant for benzothiophene photolysis was also observed.Compared with purging with nitrogen,purging seawater with oxygen evidently increased the photolysis rate of benzothiophene. Based on this observation,a benzothiophene photo-oxidation mechanism including singlet oxygen (O 2 1 Δ g) was suggested.Two photolysis products of benzothiophene were identified.The photolysis of benzothiophene is considered to be important in the removal of this compound in seawater.

Photochemistry of insecticide imidacloprid: direct and sensitized photolysis in aqueous medium

The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO 2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO 2, Cl- and NO- 3. Complete photo-oxidation of nitrogen to NO- 3 occurred very slowly via the intermediate formation of NH+ 4 and NO- 2.

Heterogeneous Photooxidation of Phenol by Catalytic Membranes

In this work the heterogenization in polymeric membranes of decatungstate,a photocatalyst for oxidation reactions,was reported.Solid state characterization techniques confirmed that the catalyst structure was preserved within the polymeric membranes.The catalytic membranes were successfully applied in the aerobic photo-oxidation of phenol,one of the main organic pollutants in wastewater,providing stable and recyclable photocatalytic systems.The dependence of the phenol degradation rate by the catalyst loading and transmembrane pressure was shown.By comparison with homogeneous reaction,the catalyst heterogenized in membrane appears to be more efficient concerning the rate of phenol photodegradation and mineralization.

Degradation of Microcystin-RR by Combination of UV/H_2O_2 Technique

The experiments were performed to investigate the degradation of microcystins in order to assess the effectiveness and feasibility of UV/H2O2 system for the disinfection of water polluted by microcystins. The influence factors such as H2O2, pH and UV light intensities were investigated respectively. Degradation of microcystin-RR （MC-RR） could be fitted by either the pseudo-first-order or second-order rate equations. This homogenous system could significantly enhance the degradation rate due to the synergetic effect between UV and H2O2. The degradation mainly followed the mechanism of direct photolysis and .OH oxidation reactions. Experimental results showed that 94.83% of MC-RR was removed under optimal experimental conditions and the UV/H2O2 system provided an alternative to promote the removal of microcystins in drinking water supplies.

Photocatalytic Oxidative Desulfurization of Gasoline by TiO_2 in[BMIm]Cu_2Cl_3 Ionic Liquid

Photocatalytic oxidative desulfurization of gasoline in [BMIm]Cu2Cl3 ionic liquid was studied. A 500-W high-pressure mercury lamp was used as the light source for irradiation, nano-TiO2 was used as the photocatalyst and air was introduced by a gas pump to supply O2 as the oxidant. Influence of the ratio of V（ionic liquid） to V（oil） and the TiO2 addition on the desulfurization rate of gasoline was investigated. An oxidative kinetics equation was founded. The results showed that the [BMIm]CUECl3 ionic liquid was an effective extractant for the desulfurization of gasoline. The appropriate TiO2 addition was 0.05 g in 50 mL of reaction mixture. The yield of desulfurized gasoline could reach 98.2% after being subjected to reaction for 2 h under the conditions of adopting a ratio of V（ionic liquid）： V（oil）=1：4, an air flow of 100 mL/min and a TiO2 addition dosage of 0.05 g. The kinetics reaction for photo-oxidation of gasoline was a first-order reaction with an apparent rate constant of 1.9664 h^-1 and a half-time of 0.3525 h.

UV Light Induced Transformation of 1-Methylnaphthalene in the Presence of Air and Its Implications for Contaminants Research

Understanding chemical transformations of contaminants and the resulting products is extremely important in devising proper monitoring methods for such contaminants and in assessing potential human exposure to the transformation products in the environment. Ultraviolet (UV) light from the sun can induce various photochemical transformations of contaminants in the environment. Alkylnaphthalenes are light-molecular-weight polycyclic aromatic hydrocarbons (PAHs) which are one of the most widespread organic pollutants present in ambient air as a result of a variety of incomplete combustion sources. In this study, 1-methylnapthalene,a typical example of an alkylnaphthalene, was subjected to UV irradiation to investigate its transformation in the presence and absence of air. Twenty-one products were detected in the reaction mixtures. Some photo-oxidation products were identified, including both ring-opened and ring-retained oxygenated compounds, such as 1-naphthaldehyde, 1-naphthoic acid, 1-naphthalenemethanol and phthalic anhydride. Although dimeric products were observed in the presence of air, more were found in the presence of helium or argon gas, indicating a different photo-oxidation pathway from those commonly observed in other media, such as water. Under just 48 hours of exposure to the UV light in the presence of air, three major products were formed with a production yield of about 10% each. Compared to 1-methylnapthalene, the UV induced transformation products observed in this study are more volatile, acidic, water soluble or toxic. The formation of these products may significantly change our understanding of the risks assessed solely from the parent compound in contaminants research and supports the inclusion of airborne transformations of the parent compound in risk assessment.

Light Panels Based on Expanded Perlite, Application as Adsorbers and Insulator against Rapid Evaporation in Subsaharien Countries

Our project concentrates on manufacture of light panels based on available natural materials (expanded perlite, sawdust and refuse of wood, vegetable coal.) mixed with a natural resin not toxic (resin of the pine). The manufacturing process permits to carry out panel’s low thickness and in various colors which give an aesthetic aspect for waste water treatment plants while preventing the emanation of the nauseous odors coming from the anaerobic metabolism of the organic matter present in the liquid effluents. Panels are also a suitable solution against rapid evaporation of stored rain fed water into lakes and dams. The particularities of these panels are especially: Lower density than water’s one, provide big capacity of adsorption for the organic gas matter, composite material acts like filter in which organic gases are photo oxidized with dioxide titanium involved in the composite material and these composite materials are insulators of basins against solar heating and consequently fast evaporation.

On the Usage of the Faraday Effect as an Authentication Technique for Vegetable Oils

In this study we report on the measurements of the Verdet constant for olive and other vegetable oils. Study of samples stored for different periods at different storage conditions showed that each olive oil sample has a Verdet constant value depending on: production year, history of the sample (i.e. storage conditions) and geographical region. Photo and auto oxidations are found to have reverse effects on the value of the measured Verdet constant, on the one hand, photo-oxidation tends to decrease the Verdet constant, but on the other hand auto-oxidation tends to increase it. It is known that oils stored in room light had significantly lower tocopherol, carotenoid, and chlorophyll contents than did the same oils kept in the dark. For other vegetable oil samples, each vegetable oil was found to have a distinct Verdet constant value. Thus it is possible to differentiate vegetable oils making use of their respective Verdet constants. Preliminary results indicated the possibility to detect olive oil adulteration using the Faraday Effect, i.e. the effect could be suggested as a food authentication technique if calibration curves and standard Verdet constants values could be prepared for comparison with those of samples under investigation.

Comparative Study of the Effects of Thermal and Photochemical Accelerated Oxidations on Quality of “Green Type” and “Black Type” French Olive Oils

Oxidative stability of two commercial olive oils of different specificity (green type and black type) has been studied during thermal and photochemical accelerated processes through the evolution of quality indices. It might help to assure a good utilisation of olive oil. In most of works described in literature, they are measured individually. In this study, a Principal Component Analysis (PCA) has been performed to emphasize their variation and describe in concise way the quality and the safety of extra-virgin olive oil after two oxidative stresses. No difference had been detected between both type oils when they are heated. Peroxides, aldehydes and conjugated dienes and trienes were formed but rapidly degraded into final oxidation compounds, mainly acid compounds. During the photochemical process, similar changes occurred slower and the green type oil had shown better stability because of its higher phenolic content. The fatty acids had been more impacted (higher disappearance of monounsaturated fatty acids (MUFA) and polyunsaturated fatty acids (PUFA)) when the oils were heated than when irradiated. Saturated fatty acids (SFA), MUFA and PUFA were the most relevant indicators to characterize non-oxidized oils and PV characterized the early stage of oil oxidation.

Desulfurization of liquid hydrocarbon fuels via Cu_2O catalyzed photooxidation coupled with liquid–liquid extraction

By combining the photochemical reaction and liquid–liquid extraction(PODS), we studied desulfurization of model fuel and FCC gasoline. The effects of air flow, illumination time, extractants, volume ratios of extractant/fuel, and catalyst amounts on the desulfurization process of PODS were analyzed in detail. Under the conditions with the air as oxidant(150 ml·min^(-1)), the mixture of DMF–water as extractant(the volume ratio of extractant/oil of 0.5) and photo-irradiation time of 2 h, the sulfur removal rate reached only 42.63% and 39.54% for the model and FCC gasoline, respectively. Under the same conditions, the sulfur removal rate increased significantly up to79% for gasoline in the presence of Cu_2O catalyst(2 g·L^(-1)). The results suggest that the PODS combined with a Cu_2O catalyst seems to be a promising alternative for sulfur removal of gasoline.

Enhancing visible-light-driven NO oxidation through molecular‐level insights of dye-loaded sea sands

Natural minerals,abundant and easily obtained through simple physical processing,offer a cost-effective and environmentally friendly solution for dyeing wastewater disposal and air pollution treatment.This study investigates the photocatalytic removal of NO using natural different types of dyes,loaded on natural sand,under visible light illumination.By examining various coating concentrations of dyes and sand weights,we discovered that sand loaded with Rhodamine B(RhB)exhibits high activity for the photo-oxidation of NO.A combination results of X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR)and thermogravimetric(TG)analyses confirm the presence of SiO_(2),CaCO_(3),Al_(2)O_(3)and iron oxides as the main components of the sand.Furthermore,studying RhB-loaded individual components reveals that CaCO_(3)plays a crucial role in enhancing the NO removal rate.Experimental results and theoretical calculations demonstrate the establishment of a directional charge transfer channel from CaCO_(3)to RhB,facilitating the adsorption and activation of molecular NO and O_(2).This work not only promotes the utilization of natural mineral resources but also enriches the fields of environmental photochemistry and semiconductor photocatalysis.