Particulate matter(PM)can cause adverse health effects by overproducing reactive oxygen species(ROS).Although the ability of PM to induce ROS generation depends on its composi-tion and environmental factors.This study...Particulate matter(PM)can cause adverse health effects by overproducing reactive oxygen species(ROS).Although the ability of PM to induce ROS generation depends on its composi-tion and environmental factors.This study explores how photo-oxidation affects ROS gen-eration from aromatic compounds(ACs,including catechol(CAT),phthalic acid(PA),and 4,4-oxydibenzoic acid(4,4-OBA))and their mixtures with transition metals(TMs,includ-ing Fe(II),Mn(II),and Cu(II))using Fourier-transform infrared(FTIR)and Ultraviolet-visible spectroscopy(UV-Vis).Results showed that photo-oxidation facilitated ROS generation from ACs.CAT-Fe(II)/Cu(II)showed synergistic effects,but 4,4-OBA-Fe(II)/Cu(II)showed antag-onistic effects.ACs-Mn(II)and PA-Fe(II)/Cu(II)exhibited synergistic effects first and then showed antagonistic effects.The different interactions were due to complexation between ACs and TMs.The photo-oxidized ACs-TMs significantly enhanced ROS generation com-pared with ACs-TMs.The study suggested the photo-oxidation mechanism involved that the transfer ofπ-electrons from the ground to an excited state in benzene rings and func-tional groups,leading to the breakage and formation of chemical bonds or easierπ-electron transfer from ACs to TMs.The former could generate ROS directly or produce polymers that promoted ROS generation,while the latter promoted ROS generation by transferringπ-electrons to dissolved oxygen quickly.Our study revealed that both interactions among components and photo-oxidation significantly influenced ROS generation.Future studies should integrate broader atmospheric factors and PM components to fully assess oxidative potential and health impacts.展开更多
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 f...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.展开更多
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 ox...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.展开更多
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 morpholog...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).展开更多
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 materia...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.展开更多
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 r...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.展开更多
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 h...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...展开更多
Supramolecular catalysis based on macrocyclic hosts can enhance the reaction rate and selectivity by leveraging their steric hindrance or nanoconfinement effects.Herein,we propose an enzyme-like supramolecular catalyt...Supramolecular catalysis based on macrocyclic hosts can enhance the reaction rate and selectivity by leveraging their steric hindrance or nanoconfinement effects.Herein,we propose an enzyme-like supramolecular catalytic system by combining the nanocavity of cucurbit[8]uril(CB[8])with the photoactivation ability of photoinduced electron transfer(PET),in order to effectively activate substrates into reactive intermediates.The supramolecular catalyst,a host–vip complex of CB[8]and a viologen derivative,recognized and activated benzyl alcohol substrates into reactive ketyl radicals through the host-promoted PET process.In the meantime,the generation of oxidant O_(2)^(·-)was also enhanced.As a result,the photo-oxidation of benzyl alcohol to aldehyde was greatly facilitated with remarkable yield(90%–99%)for substrates with varied substituents and molecular backbones.The benzyl aldehyde products could be replaced by benzyl alcohol substrates from supramolecular catalysts due to their reduced binding affinity,contributing to a highly efficient catalytic cycle.Interestingly,owing to the activation of benzyl alcohol moiety,an unusual preference for oxidizing hydroxyl groups over sulfide groups could be realized.This supramolecular catalytic system demonstrates superior efficiency and selectivity,offering a facile yet effective design strategy for supramolecular catalysis and expanding the toolkit for photocatalysis.展开更多
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 a...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.展开更多
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, chemic...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.展开更多
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 repr...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.展开更多
Aerosol hygroscopicity and liquid water content(ALWC)have important influences on the environmental and climate effect of aerosols.In this study,we measured the hygroscopic growth factors(GF)of particles with dry diam...Aerosol hygroscopicity and liquid water content(ALWC)have important influences on the environmental and climate effect of aerosols.In this study,we measured the hygroscopic growth factors(GF)of particles with dry diameters of 40,80,150,and 200 nm during the wintertime in Nanjing.Both the GF-derived hygroscopicity parameter(κ_(gf))and ALWC increased with particle size,but displayed differing diurnal variations,withκ_(gf)peaking around the midday,while ALWC peaking in the early morning.Nitrate,ammonium and oxygenated organic aerosols(OOA)were found as the chemical components mostly strongly correlated with ALWC.A closure study suggests that during midday photo-oxidation and nighttime high ALWC periods,theκof organic aerosols(κ_(org))was underestimated when using previous parameterizations.Accordingly,we re-constructed parameterizations forκ_(org)and the oxidation level of organics for these periods,which indicates a higher hygroscopicity of photochemically formed OOA than the aqueous OOA,yet both being much higher than the generally assumed OOA hygroscopicity.Additionally,in a typical high ALWC episode,concurrently increased ALWC,nitrate,OOA as well as aerosol surface area and mass concentrations were observed under elevated ambient RH.This strongly indicates a coupled effect that the hygroscopic secondary aerosols,in particular nitratewith strong hygroscopicity,led to large increase in ALWC,which in turn synergistically boosted nitrate and OOA formation by heterogeneous/aqueous reactions.Such interaction may represent an important mechanism contributing to enhanced formation of secondary aerosols and rapid growth of fine particulate matter under relatively high RH conditions.展开更多
Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China.Thus,a large-scale outdoor atmospheric simulation smog chamber ...Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China.Thus,a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences(the CRAES Chamber),which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment.The chamber consisted of a 56-m^(3) fluorinated ethylene propylene(FEP) Teflon film reactor,an electrically-driven stainless steel alloy shield,an auxiliary system,and multiple detection instrumentations.By performing a series of characterization experiments,we obtained basic parameters of the CRAES chamber,such as the mixing ability,the background reactivity,and the wall loss rates of gaseous compounds(propene,NO,NO_(2),ozone) and aerosols(ammonium sulfate).Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol(SOA),including α-pinene ozonolysis,propene and 1,3,5-trimethylbenzene photooxidation.Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work:higher temperature and the presence of seed could reduce the vapor wall loss;SOA yield was found to depend inversely on temperature,and the presence of seed could increase SOA yield.The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls.The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.展开更多
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 inte...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.展开更多
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 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.展开更多
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 preserve...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.展开更多
Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of u...Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of unstable nitrate species causes desorption to release NO_(2).In this study,SnO_(2) quantum dots and oxygen vacancies co-modified Zn_(2)SnO_(4)(ZSO-SnO_(2)-OVs)were prepared by a one-step hydrothermal procedure,the NO photo-oxidation was investigated by a combination of solid experimental and theoretical support.Impressively,spectroscopic measurements indicate that fast carrier dynamics can be achieved due to the electron transfer efficiency of ZSO-SnO_(2)-OVs reaching 99.99%,far outperforming the counterpart and previously reported photocatalysts.During NO oxidation,molecular NO/O_(2) and H2O are efficiently adsorbed/activated around OVs and SnO_(2) QDs,respectively.In-situ infrared measurements and calculated electron localized function disclose two main findings:(1)richly electrons enable NO promptly form NOinstead of toxic NO_(2) or NO^(+);(2)the generation of stable and undecomposed bidentate NO_(3)rather than bridging or monodentate one benefits the deep oxidation of NO via shifting reaction sites from O terminals for original ZSO to Sn ones for ZSO-SnO_(2)-OVs.The synergistic action of SnO_(2) QDs and OVs positively contributes to the NO oxidation performance enhancement(60.6%,0.1 g of sample)and high selectivity of NO to NO_(3)(99.2%).Results from this study advance the mechanistic understanding of NO photooxidation and its selectivity to NO_(3)over photocatalysts.展开更多
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 influenc...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.展开更多
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 a...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.展开更多
To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite（M-ZnO） was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ul...To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite（M-ZnO） was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.展开更多
基金supported by the Weiqiao-UCAS Special Projects on Low-Carbon Technology Development(No.GYY-DTFZ-2022-007)the Fundamental Research Funds for the Central Universities(No.E0E48927×2)the National Natural Science Foundation of China(No.21677145).
文摘Particulate matter(PM)can cause adverse health effects by overproducing reactive oxygen species(ROS).Although the ability of PM to induce ROS generation depends on its composi-tion and environmental factors.This study explores how photo-oxidation affects ROS gen-eration from aromatic compounds(ACs,including catechol(CAT),phthalic acid(PA),and 4,4-oxydibenzoic acid(4,4-OBA))and their mixtures with transition metals(TMs,includ-ing Fe(II),Mn(II),and Cu(II))using Fourier-transform infrared(FTIR)and Ultraviolet-visible spectroscopy(UV-Vis).Results showed that photo-oxidation facilitated ROS generation from ACs.CAT-Fe(II)/Cu(II)showed synergistic effects,but 4,4-OBA-Fe(II)/Cu(II)showed antag-onistic effects.ACs-Mn(II)and PA-Fe(II)/Cu(II)exhibited synergistic effects first and then showed antagonistic effects.The different interactions were due to complexation between ACs and TMs.The photo-oxidized ACs-TMs significantly enhanced ROS generation com-pared with ACs-TMs.The study suggested the photo-oxidation mechanism involved that the transfer ofπ-electrons from the ground to an excited state in benzene rings and func-tional groups,leading to the breakage and formation of chemical bonds or easierπ-electron transfer from ACs to TMs.The former could generate ROS directly or produce polymers that promoted ROS generation,while the latter promoted ROS generation by transferringπ-electrons to dissolved oxygen quickly.Our study revealed that both interactions among components and photo-oxidation significantly influenced ROS generation.Future studies should integrate broader atmospheric factors and PM components to fully assess oxidative potential and health impacts.
基金Science and Technology Development Planning Foundation of Jilin Province, China(No.20030405)
文摘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.
基金supported by the National Program on Key Basic Research Project (2016YFA0203000)the Early Career Scheme (ECS 809813) from the Research Grant Council, Hong Kong SAR Government+2 种基金the Croucher Foundation Visitorship for PRC Scholars 2015/16 at The Education University of Hong Kongthe National Natural Science Foundation of China (51672312, 21373275)the Program for New Century Excellent Talents in University (NCET-12-0668)~~
文摘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.
基金financially supported by the National Key R&D Program of China(No.2018YFB0605502)the National Natural Science Foundation of China(No.U1560104)the National Environmental Corrosion Platform(NECP)。
文摘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).
基金financially supported by the National Natural Science Foundation of China (No. 51673111)
文摘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.
文摘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.
基金the National Natural Science Foundation of China (No.20704040).
文摘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...
基金supported financially by the National Natural Science Foundation of China(grant nos.22193020,22193021,and 21821001).
文摘Supramolecular catalysis based on macrocyclic hosts can enhance the reaction rate and selectivity by leveraging their steric hindrance or nanoconfinement effects.Herein,we propose an enzyme-like supramolecular catalytic system by combining the nanocavity of cucurbit[8]uril(CB[8])with the photoactivation ability of photoinduced electron transfer(PET),in order to effectively activate substrates into reactive intermediates.The supramolecular catalyst,a host–vip complex of CB[8]and a viologen derivative,recognized and activated benzyl alcohol substrates into reactive ketyl radicals through the host-promoted PET process.In the meantime,the generation of oxidant O_(2)^(·-)was also enhanced.As a result,the photo-oxidation of benzyl alcohol to aldehyde was greatly facilitated with remarkable yield(90%–99%)for substrates with varied substituents and molecular backbones.The benzyl aldehyde products could be replaced by benzyl alcohol substrates from supramolecular catalysts due to their reduced binding affinity,contributing to a highly efficient catalytic cycle.Interestingly,owing to the activation of benzyl alcohol moiety,an unusual preference for oxidizing hydroxyl groups over sulfide groups could be realized.This supramolecular catalytic system demonstrates superior efficiency and selectivity,offering a facile yet effective design strategy for supramolecular catalysis and expanding the toolkit for photocatalysis.
文摘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.
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.42275116 and 41975172).
文摘Aerosol hygroscopicity and liquid water content(ALWC)have important influences on the environmental and climate effect of aerosols.In this study,we measured the hygroscopic growth factors(GF)of particles with dry diameters of 40,80,150,and 200 nm during the wintertime in Nanjing.Both the GF-derived hygroscopicity parameter(κ_(gf))and ALWC increased with particle size,but displayed differing diurnal variations,withκ_(gf)peaking around the midday,while ALWC peaking in the early morning.Nitrate,ammonium and oxygenated organic aerosols(OOA)were found as the chemical components mostly strongly correlated with ALWC.A closure study suggests that during midday photo-oxidation and nighttime high ALWC periods,theκof organic aerosols(κ_(org))was underestimated when using previous parameterizations.Accordingly,we re-constructed parameterizations forκ_(org)and the oxidation level of organics for these periods,which indicates a higher hygroscopicity of photochemically formed OOA than the aqueous OOA,yet both being much higher than the generally assumed OOA hygroscopicity.Additionally,in a typical high ALWC episode,concurrently increased ALWC,nitrate,OOA as well as aerosol surface area and mass concentrations were observed under elevated ambient RH.This strongly indicates a coupled effect that the hygroscopic secondary aerosols,in particular nitratewith strong hygroscopicity,led to large increase in ALWC,which in turn synergistically boosted nitrate and OOA formation by heterogeneous/aqueous reactions.Such interaction may represent an important mechanism contributing to enhanced formation of secondary aerosols and rapid growth of fine particulate matter under relatively high RH conditions.
基金supported by the China Postdoctoral Science Foundation (No.2019M660752)the Beijing Municipal Science&Technology Commission (No.Z181100005418015),LAC/CMA (No.2019B08)+2 种基金the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of ChinaChinese Research Academy of Environmental Sciences (Nos.GYG5051201,2009GGQD18,2019YSKY-018,2019YSKY-012)the Chinese Academy of Sciences Strategic Leading Science and Technology Project (Class B)(No.XDB05010200)。
文摘Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China.Thus,a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences(the CRAES Chamber),which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment.The chamber consisted of a 56-m^(3) fluorinated ethylene propylene(FEP) Teflon film reactor,an electrically-driven stainless steel alloy shield,an auxiliary system,and multiple detection instrumentations.By performing a series of characterization experiments,we obtained basic parameters of the CRAES chamber,such as the mixing ability,the background reactivity,and the wall loss rates of gaseous compounds(propene,NO,NO_(2),ozone) and aerosols(ammonium sulfate).Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol(SOA),including α-pinene ozonolysis,propene and 1,3,5-trimethylbenzene photooxidation.Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work:higher temperature and the presence of seed could reduce the vapor wall loss;SOA yield was found to depend inversely on temperature,and the presence of seed could increase SOA yield.The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls.The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.
文摘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.
文摘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.
基金Financial support from the"Ministero dell’Istruzione dell’Università e della Ricerca"(MIUR)(CEMIF.CAL-CLAB01TYEF and CAMERE-RBNE03JCR5)is gratefully acknowledged.
文摘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.
基金the National Natural Science Foundation of China(Grant No.51808080)China Postdoctoral Science Foundation(No.2022M710830)+4 种基金Venture and Innovation Support Program for Chongqing Overseas Returnees(No.cx2022005)the Natural Science Foundation Project of CQ CSTC(No.CSTB2022NSCQ-MSX1267)Research Project of Chongqing Education Commission Foundation(No.KJQN201800826)Science and Technology Research Program of Chongqing Municipal Education Commission of China(No.KJZD-K202100801)Post-doctoral Program Funded by Chongqing,and Chongqing University Innovation Research Group project(No.CXQT21023).
文摘Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of unstable nitrate species causes desorption to release NO_(2).In this study,SnO_(2) quantum dots and oxygen vacancies co-modified Zn_(2)SnO_(4)(ZSO-SnO_(2)-OVs)were prepared by a one-step hydrothermal procedure,the NO photo-oxidation was investigated by a combination of solid experimental and theoretical support.Impressively,spectroscopic measurements indicate that fast carrier dynamics can be achieved due to the electron transfer efficiency of ZSO-SnO_(2)-OVs reaching 99.99%,far outperforming the counterpart and previously reported photocatalysts.During NO oxidation,molecular NO/O_(2) and H2O are efficiently adsorbed/activated around OVs and SnO_(2) QDs,respectively.In-situ infrared measurements and calculated electron localized function disclose two main findings:(1)richly electrons enable NO promptly form NOinstead of toxic NO_(2) or NO^(+);(2)the generation of stable and undecomposed bidentate NO_(3)rather than bridging or monodentate one benefits the deep oxidation of NO via shifting reaction sites from O terminals for original ZSO to Sn ones for ZSO-SnO_(2)-OVs.The synergistic action of SnO_(2) QDs and OVs positively contributes to the NO oxidation performance enhancement(60.6%,0.1 g of sample)and high selectivity of NO to NO_(3)(99.2%).Results from this study advance the mechanistic understanding of NO photooxidation and its selectivity to NO_(3)over photocatalysts.
文摘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.
基金the Research Foundation of Hebei Province Education Department(2007440)
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.51173208 and 51373202)the Natural Science Foundation of Guangdong(No.S2011020001212)
文摘To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite（M-ZnO） was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.
