Visible-light-induced photocatalytic degradation of 4-chlorophenol and phenolic compounds in aqueous suspension of pure titania: demonstrating the existence of a surface-complex-mediated path

The visible-light-induced degradation reaction of 4-chlorophenol (4-CP) was investigated in aqueous suspension of pure TiO2. Contrary to common expectations, 4-CP could be degraded under visible illumination (lambda > 420 nm), generating chlorides and CO2 concomitantly. The observed visible reactivity was not due to the presence of trace UV light since the visible-light-induced reactions exhibited behaviors distinguished from those of UV-induced reactions. Dichloroacetate could not be degraded under visible light, whereas it degraded with a much faster rate than 4-CP under UV irradiation. The addition of tert-butyl alcohol, a common OH radical scavenger, did not affect the visible reactivity of 4-CP, which indicates that OH radicals are not involved. Other phenolic compounds such as phenol and 2,4-dichlorophenol were similarly degraded under visible light. The surface complexation between phenolic compounds and TiO2 appears to be responsible for the visible light reactivity. Diffuse reflectance UV-vis spectra showed that 4-CP adsorbed on TiO2 powder induced visible light absorption. The visible light reactivity among several TiO2 samples was apparently correlated with the surface area of TiO2. The visible-light-induced photocurrents on a TiO2 electrode could be obtained only in the presence of 4-CP. It is proposed that a direct electron transfer from surface-complexed phenol to the conduction band of TiO2 upon absorbing visible light (through ligand-to-metal charge transfer) initiates the oxidative degradation of phenolic compounds. When the surface complex formation was hindered by surface fluorination, surface platinization, and high pH, the visible-light-induced degradation of 4-CP was inhibited. The evidence of visible-light-induced reactions and the experimental conditions affecting the visible reactivity were discussed in detail.     

Visible-light induced water detoxification catalyzed by PtII dye sensitized titania

A new dye sensitization system incorporating Pt(dcbpy)Cl2 on Degussa P-25 TiO2 for the photomineralization of aqueous organic pollutants under visible light irradiation is described. The representative wastewater pollutant, 4-chlorophenol (4-CP), is readily oxidized (ultimately to CO2) when the PtII dye sensitized TiO2 is exposed to visible light in the presence of dissolved O2, and the reaction is accelerated when the solution is purged with O2 gas at 1 atm. The sensitizer is regenerated during the photocatalysis; therefore, 4-CP effectively reduces the oxidized form of the surface bound dye. The experimental data are consistent with parallel oxidative decomposition pathways for 4-CP, one which operates using conduction band electrons to produce hydroxyl radicals and another where the oxidized sensitizer irreversibly oxidizes 4-CP.     

A Novel Kinetic Approach for Photocatalytic Degradation of Azo Dye with CdS and Ag/CdS Nanoparticles Fixed on a Cement Bed in a Continuous‐Flow Photoreactor

Azo dyes are one of the synthetic dyes that have been used in many textile industries. Azo dye and their intermediate products are toxic, carcinogenic, and mutagenic to aquatic life. Removal of azo dyes is one of the main challenges before releasing the wastes discharged by textile industries. Photocatalytic degradation of azo dyes by nanoparticles is one of the environment‐friendly methods used for the removal of dyes from textile effluents. Therefore, this study focused on degradation of azo dye, Direct Red 264. Photocatalytic degradation of DR 264 azo dye was investigated using CdS and Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor under UV‐C exposure. The effect of the parameters of type and mass of catalyst, temperature, flow rate, dye concentration, and light intensity were evaluated for azo dye removal. Under optimal conditions, photocatalytic degradation of DR 264 azo dye using Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor obtained an efficiency of 99.99%. A developed kinetic model was proposed based on the intrinsic elementary reactions. The proposed model is in a good agreement with the Langmuir–Hinshelwood (L–H) equation. The pseudo–steady‐state approximation has considered for the concentration of hydroxyl radicals associated with the L–H model under certain conditions and explains consistently the dependence of the apparent kinetic parameter, k_obs (the reaction rate constant), and K_R (the adsorption equilibrium constant) with the light intensity. Based on the model, k_obs for Ag/CdS was greater than the CdS nanoparticles.     

Degradation of 4-chlorophenol in aqueous solution by γ-radiation and ozone oxidation

The degradation of 4-chlorophenol (4-CP) by using gamma rays generated by a ⁶⁰Co source in the presence of O₃ was investigated. The radiolysis of 4-CP and the kinetics of 4-CP mineralization were analyzed based on the determination of total organic carbon (TOC). The influence of initial 4-CP concentration and the free radicals scavengers (such as NaHCO₃ and t-butanol) on the 4-CP degradation was also studied. The results showed that when the radiation rate was 336 Gy·min⁻¹, 4-chlorophenol at concentration of 10 mg·L⁻¹ could be completely degraded at the radiation dose of 2 kGy. The degradation of 4-chlorophenol could be described by a first-order reaction model, the rate constant of 4-CP degradation by combined ozonation and radiation was 0.1016 min⁻¹, which was 2.4 times higher than the sum of radiation (0.0294 min⁻¹) and ozonation (0.0137 min⁻¹). It revealed that the combination of radiation and ozonation resulted in synergistic effect, which can remarkably increase the degradation efficiency of 4-CP.     

Photocatalytic degradation of 4-chlorophenol: A mechanistically-based model

The photocatalytic degradation of 4-CP was mathematically modelled using the mechanistic insights and data presented in an earlier study [1]. The solution and surface concentrations of reacting species were calculated by solving a system of differential equations that account for oxidation reactions of dissolved and adsorbed species, adsorption and desorption, reduction of oxygen, and hole-electron recombination. The differential equations were integrated over discrete time-periods and annular regions of the photoreactor. The resulting model predicts the trends observed in studies in other laboratories using different experimental apparati. Using the model it is possible to predict effects of reactor geometry, TiO₂ loading, light intensity, and mixing on the course of TiO₂ photocatalytic oxidation. The model verifies the importance of surface reactions, and reveals the need to better understand the fate and role of oxygen in TiO₂ photocatalytic systems.     

节能发光二极管照射下光催化降解染料的最新进展(英文)

Light emitting diodes(LEDs) are gaining recognition as a convenient and energy-efficient light source for photocatalytic application. This review focuses on recent progress in the research and development of the degradation of dyes in water under LED light irradiation and provides a brief overview of photocatalysis, details of the LEDs commonly employed, a discussion of the advantages of LEDs over traditional ultraviolet sources and their application to photocatalytic dye degradation. We also discuss the experimental conditions used, the reported mechanisms of dye degradation and the various photocatalytic reactor designs and pay attention to the different types of LEDs used, and their power consumption. Based on a literature survey, the feasibility, benefits, limitations, and future prospects of LEDs for use in photocatalytic dye degradation are discussed in detail.     

Efficient photosensitized degradation of 4-chlorophenol over immobilized aluminum tetrasulfophthalocyanine in the presence of hydrogen peroxide

The photosensitized degradation of 4-chlorophenol (4-CP) under visible light (lambda > or = 450 nm) irradiation in an aerated aqueous medium at pH 12 was studied using an immobilized photosensitizer, aluminum tetrasulfophthalocyanine, on a commercial resin Amberlite IRA 400. The catalyst exhibited strong adsorption toward 4-CP, but the adsorption led to an exponential decrease in both the initial rate and the apparent first-order rate constant, as measured by 4-CP loss in the bulk solution. Several intermediates were formed from 4-CP oxidation, including fumaric acid, benzoquinone, and hydroquinone, which were adsorbed strongly on the catalyst and lowered the photosensitized reaction. Addition of H2O2 was found to be an efficient way to eliminate the colored intermediates and consequently recover the catalyst activity. The immobilized sensitizer was stable and could be used repeatedly in the presence of H2O2. The optimal loading of the photosensitizer in the catalyst was about 1.0 wt %.     

Abatement of volatile organic compounds using an annular photocatalytic reactor: Study of gaseous acetone

Photocatalytic oxidation of organic compounds in gas phase appears to be a promising process for remediation of polluted air. In the present work, the photocatalytic degradation of acetone, which is a typical pollutant of indoor air, was investigated by using an annular photoreactor. After a modelling by a cascade of elementary continuously stirred tank reactor, the annular photoreactor was assimilated to a plug flow reactor (PFR). No transfer limitation (external and internal) has been demonstrated for this reactor with the fibreglass photocatalytic support. The influence of several kinetic parameters has been studied such as pollutant concentration, incident light irradiance, contact time and humidity content. The Langmuir–Hinshelwood model has been verified for acetone. It can be noticed that no by-products have been detected by FID suggesting almost total mineralization. The possible minor gaseous by-products have been accumulated into a mixture of ethanol–liquid nitrogen at −50 °C then a sample of it has been injected into a GC/MS for analysis. A mechanistic pathway is then proposed for the photocatalytic degradation of acetone.     

Mechanism and kinetics of 2-chlorophenol degradation in drinking water by photo-electrochemical synergic effect

As the important parts of advanced oxidation processes (AOPs), photocatalysis and electrocatalysis technologies have a good applicative promising in the removal of micropollutants from water. But it is unpractical for photocatalysis with the catalytic reaction rate, the immobilization of catalyst, and the stability aspects, etc.[1—3]. One of the vital faults for the application of electrocatalysis for removal organics is electrode fouling [4]. The anodic direct electrons transfer reactions p…     

185nm UV降解水中4-CP、4-NP和Rh B的研究

本文以对氯苯酚(4-CP)、对硝基苯酚(4-NP)和罗丹明B(Rh B)为模型有机物(以4-CP和4-NP为小分子模型有机物,以Rh B为大分子模型有机物),分别研究了185 nm UV对水中这3种模型有机物的降解规律、性能和效果.研究结果表明,185 nm UV直接对水中4-CP、4-NP和Rh B有很好的降解效果.研究内容包括:185 nm UV降解模型有机物的浓度、TOC(Total organic carbon)浓度、185 nm UV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面.     

Visible-light detoxification and charge generation by transition metal chloride modified titania

Amorphous microporous metal oxides of titanium (AMM-Ti) modified with chlorides of PtIV, IrIV, RhIII, AuIII, PdII, CoII, and NiII have been prepared by the sol-gel method and characterized by various surface analytical methods. These hybrid AMM-Ti powders are catalysts for the photodegradation of 4-chlorophenol (4-CP) in aqueous solution when illuminated with visible (lambda > or = 400 or 455 nm) or UV (lambda > or = 335 nm) light. The initial rate depends on the dopant level and is highest at 3.0% Pt in the case of PtIV/AMM-Ti. When employed in a photoelectrochemical cell, the activity spectrum of the photocurrent extends downward to about 600 nm, as does the photodegradation of 4-CP. It is suggested that the metal salt acts as a redox-active chromophore, transmitting the photogenerated charges to the amorphous matrix.     

Photoinduced degradation of orange II on different iron (hydr)oxides in aqueous suspension: rate enhancement on addition of hydrogen peroxide, silver nitrate, and sodium fluoride

Photoinduced organic oxidation with iron (hydr)oxides in aqueous suspension has been argued with respect to two principal mechanisms: (a) photoinduced ligand-to-metal charge transfer within a surface complex and (b) semiconductor photocatalysis. In this work, the photodegradation of azo dye orange II with UV light (lambda > or = 320 nm) in the aerated aqueous suspensions of haematite, maghemite, magnetite, goethite, lepidocrocite, and feroxyhite at an initial pH of 6.5 has been examined. The results showed that (1) all of the catalysts were effective at initiating dye photodegradation but the iron oxides appeared to be more active than the iron hydroxides; (2) the photodissolution of different iron phases and the dye photolysis in the dissolved iron solutions were very slow; (3) the initial rate of dye loss was proportional to the initial amount of adsorption, implying dye photodegradation on the catalyst surface; and (4) upon addition of H2O2, AgNO3, and NaF to the suspension, the rate of dye photodegradation was significantly enhanced with all the catalysts. In the presence of H2O2, less than 50% of the total rate enhancement was ascribed to the photo-Fenton reaction in solution and the dark Fenton reactions in solution and on the catalyst. In the presence of AgNO3, about 1 mole of silver particles was produced by consuming 3 moles of the dye substrate. In the presence of NaF, hydroxyl radicals were detected by an ethanol scavenger, whereas such radicals were not found in the absence of NaF. Moreover, under visible-light irradiation (lambda > or = 450 nm), the dye degradation was much slower than that under UV irradiation, but the reaction was also accelerated by the addition of NaF and AgNO3. The results suggest that mechanism b, not mechanism a, is operative for dye photodegradation occurring on the iron (hydr)oxides. A detailed discussion of all possible pathways is given in the text.     

Visible light-excited surface plasmon resonance charge transfer significantly improves the photocatalytic activities of ZnO semiconductor for pollutants degradation

To effectively address environmental pollution, we synthesized Au-loaded ZnO nanocomposites and applied for the photocatalytic degradation of 2-chlorophenol (2-CP) under visible light irradiation. The as-prepared nanophotocatalysts delivered much improved photocatalytic degradation activities as compared to the bare ZnO nanoparticles and 32% of the pollutant was degraded with 2AuZnO in 1 hr. These improved photoactivities are attributed to the extended visible light absorption due to the surface plasmon resonance property of the loaded Au nanoparticles. Moreover, Au nanoparticles played important role in charge separation by inducting excited electrons to the conduction band of ZnO photocatalyst and surface catalysis as confirmed from photoluminescence spectra and amount of the generated hydroxyl radicals. The trapping experiments confirmed that positive holes were the major degrading species during the photocatalytic degradation of 2-CP. This work provides a feasible way to improve the photocatalysis by introducing a proper amount of noble metals over the surface of semiconductor photocatalysts.     

Hydrogen production and photocatalytic activity of g-C3N4/Co-MOF (ZIF-67) nanocomposite under visible light irradiation

Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C₃N₄ nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C₃N₄ surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C₃N₄/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H₂) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H₂ production of the g-C₃N₄/ZIF-67 composite was 2084 μmol g⁻¹, which is 3.84 folds greater than that of bare g-C₃N₄ (541 μmol g⁻¹).     

在Cr(Ⅵ)和4-氯酚复合污染系统中多孔石墨相氮化碳的协同光催化效应

随着工农业的迅速发展,多组分复合污染系统广泛分布于自然环境中,例如电镀废水、污水处理厂污泥、城市生活垃圾等.自1972年光催化劈裂水产氢被发现以来,光催化技术已被广泛应用于解决环境污染问题.一方面,光生电子在酸性条件下能将重铬酸根(Cr2O72–)中高毒性的Cr(VI)还原成低毒性的Cr(Ⅲ).另一方面,水中有机污染物通过光催化氧化过程可被降解为二氧化碳和水.然而在目前的光催化领域,大部分研究者专注于新型光催化剂的开发,并在单组份光催化系统中测试所开发材料的光催化活性,而忽视了蕴藏在光催化反应本身中的科学问题.事实上,将光催化技术应用于复合污染系统具有非常大的现实意义.少数研究者试图通过光催化过程处理多组分废水.然而,在复合污染系统中的协同光催化效应和机理尚未明确.近几年,基于可见光响应、环境友好、成本低等优点,作为一种不含金属的半导体光催化剂,石墨相氮化碳(g-C3N4)已被广泛应用于环境光催化领域.然而在实际应用中,g-C3N4的光催化活性却较差,因为聚集态层状结构不但限制了光生载流子的表面迁移,而且还增加了光催化反应的传质阻力.因此,人们尝试形貌控制策略来提高g-C3N4的光催化活性,例如氮化碳纳米片、空心球、量子点的构建.在前期工作中,我们通过一种简单的前驱体预处理策略使用盐酸和乙二醇共处理的三聚氰胺作原料成功制备出了多孔石墨相氮化碳(pg-C3N4),因其具有丰富的多孔微观结构而表现出了卓越的光催化活性.本文初步研究了在酸性条件下使用所制备g-C3N4或pg-C3N4光催化还原水中Cr(Ⅵ)成Cr(Ⅲ)的反应.然后在不同pH条件下进一步研究了在Cr(Ⅵ)和4-氯酚(4-CP)复合污染系统中的协同光催化效应.结果发现,与单组分光催化系统相比,在Cr(Ⅵ)和4-CP复合污染系统中Cr(Ⅵ)的还原效率和4-CP的降解效率同时提高,即在Cr(Ⅵ)和4-CP复合污染系统中存在协同光催化效应.最后讨论了在Cr(Ⅵ)和4-CP复合污染系统中的协同光催化效应可归因于pg-C3N4的电子转移作用加速了Cr2O72–和4-CP之间的氧化还原反应.在用稀H2SO4调节pH至3的Cr(VI)和4-CP复合污染系统中,由于Cr2O72–中氧原子的电子云密度较低,因此Cr2O72–和4-CP之间的氧化还原反应通过pg-C3N4的电子转移作用易于进行,因而表现出明显的协同光催化效应.     

Synthesis of 7H-indolo[1,2-a]quinolinium derivatives via oxidative photocyclization of 3H-indolium salts using blue LED photoreactor

Oxidative photocyclization of 1-phenyl-2-(2-arylethenyl)-3,3-dimethyl-3H-indolium perchlorates leading to 7H-indolo[1,2-a]quinolinium salts was investigated. The synthesis was performed under Vis irradiation. Blue LEDs emitting at 454.5 nm were used as the light source. The reaction progress was followed by UV-Vis spectroscopy. The products were characterized by IR, ¹H and ¹³C NMR spectroscopy. Reaction time depended on the position of the UV-Vis absorption band of both the substrates and products. The results revealed that the application of blue LED photoreactor makes the synthesis of 7H-indolo[1,2-a]quinolinium easier and more convenient.     

Scaling Up of a Photoreactor for Formic Acid Degradation Employing Hydrogen Peroxide and UV Radiation

A model for scaling up a homogeneous photoreactor was developed and experimentally verified in a pilot‐plant‐size apparatus. The procedure is exemplified by the oxidation of dilute aqueous HCOOH solutions with UV radiation (254 nm) and H₂O₂. First, the kinetic model and the kinetic parameters of the HCOOH degradation were obtained in a well‐stirred, small, batch flat‐plate photoreactor (volume=70 ml). The method employed in the analysis of the experimental results yielded reaction‐rate expressions for HCOOH and H₂O₂ that were independent of the reactor configuration. These kinetic equations and the corresponding kinetic constants were then used in a mathematical, fully deterministic model of a continuous‐flow, 2‐m‐long, annular reactor (0.0065 m² of cross section for flow) operating in a laminar‐flow regime to predict exit concentrations of HCOOH. Irradiation was provided in both cases by two different types of germicidal lamps. No additional experiments were made to adjust the reactor‐model parameters. Theoretical predictions from the representation of the reactor performance obtained were compared with experimental data furnished by experiments in the much‐larger‐size, cylindrical‐flow reactor. Results showed good agreement for the range of variables explored; they corresponded to expected operating conditions in water streams polluted with low concentrations of organic compounds.     

Reaction CH(3) + OH Studied over the 294-714 K Temperature and 1-100 bar Pressure Ranges

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).     

Determination of the light-induced degradation rate of the solar cell sensitizer N719 on TiO2 nanocrystalline particles

The oxidative degradation rate, kdeg, of the solar cell dye (Bu4N+)2[Ru(dcbpyH)2(NCS)2]2-, referred to as N719 or [RuL2(NCS)2], was obtained by applying a simple model system. Colloidal solutions of N719-dyed TiO2 particles in acetonitrile were irradiated with 532-nm monochromatic light, and the sum of the quantum yields for the oxidative degradation products [RuL2(CN)2], [RuL2(NCS)(CN)], and [RuL2(NCS)(ACN)], Phideg, was obtained at eight different light intensities in the range of 0.1-16.30 mW/cm2 by LC-UV-MS. The Phideg values decreased from 3.3 x 10-3 to 2.0 x 10-4 in the applied intensity range. By using the relation kdeg = Phidegkback and back electron-transfer reaction rates, kback, obtained with photoinduced absorption spectroscopy, it was possible to calculate an average value for the oxidative degradation rate of N719 dye attached to TiO2 particles, kdeg = 4.0 x 10-2 s-1. The stability of N719 dye during solar cell operation was discussed based on this number, and on values of the electron-transfer rate between [Ru(III)L2(NCS)2] and iodide ion that are available in the literature.     

Infrared electroluminescence of organic nanocrystals in polymer composites

Electroluminescent polymeric nanocomposite structures that are based on aromatic polyimides and cyanine dye nanosized crystals known as J aggregates and emit light in the IR region were prepared. For the first time, doped polymer systems were found to display IR luminescence whose spectrum had the form of a very narrow band that peaked at 1100 nm. Nanosized J-aggregate crystals in these new polymer materials act not only as effective acceptors of energy of excitonic states but also as active electron-hole transport sites.