Enhanced photocatalytic degradation of monocrotophos in aqueous solution over titania hybridised with beta-zeolite

Photocatalytic degradation of monocrotophos has been carried out in a slurry type batch reactor. The reaction variables were optimised to obtain maximum degradation efficiency. The degradation rate of monocrotophos is significantly higher for acidic solutions than for alkaline solutions. It is also observed that the high concentration environment of the pollutant formed around the hybridised TiO2, enhances the mineralisation rate of monocrotophos. Hence an increase in relative photonic efficiency is obtained.     

Probing photocatalytic reactions in semiconductor systems: Study of the chemical intermediates in 4 -chlorophenol degradation by a variety of methods

The photocatalytic transformation of 4-chlorophenol (4-CP) has been studied in aqueous slurries, on powders and on immobilized particulate films of TiO₂. These results are compared to those obtained using gamma and pulse radiolysis in order to establish a comprehensive picture of the 4-CP reaction pathway in TiO₂ systems. The disappearance of 4-CP and its reaction intermediates in TiO₂ slurries involves a combination of hydroxyl radical oxidation, direct electron transfer and surface chemical reactions.     

光催化降解过程中苯酚的分光光度法测定

提出了用双波长紫外分光光度法测定含对苯醌和苯酚混合液中苯酚的方法,解决了用分光光度法直接测定苯酚时对苯醌分析的干扰。选择测定波长为270和292nm。用于纳米二氧化钛光催化降解苯酚过程中苯酚的测定。标准样品的加标回收率为：99.79％～101．17％,相对标准偏差小于0．50％;样品测定的加标回收率为：99．14％～104．75％,相对标准偏差小于2．20％,苯酚的检出限为0．10mg／L。     

Heterogeneous photocatalyzed degradation of a pesticide derivative, 3-chloro-4-methoxyaniline, in aqueous suspensions of titania

The photocatalyzed degradation of a pesticide derivative, 3-chloro-4-methoxyaniline (1), has been investigated in aqueous suspensions of titanium dioxide (TiO₂) and air as a function of irradiation time under a variety of conditions using UV?CVis spectroscopic and HPLC analysis techniques. The degradation kinetics were studied under different conditions such as types of TiO₂ powders, reaction pH, catalyst loading, substrate, and H₂O₂ concentrations. The photocatalyst Degussa P25 showed better photocatalytic activity for the degradation of the compound 1. Addition of hydrogen peroxide as an electron acceptor in addition to oxygen greatly enhanced the degradation rate of the compound 1. Higher degradation rates were observed at lower and higher pH values, i.e., 3.15 and 9.15, respectively. The optimal substrate concentration and catalyst loading for the degradation was found to be 0.6?mM with 1.5?g?L^?1. A probable pathway for the decomposition of compound 1 is proposed.     

The mechanism and pathway of the ozonation of 4-chlorophenol in aqueous solution

Chlorophenols (CPs) have been widely used in dif- ferent formulations as preservatives, herbicides, insec- ticides, bactericides and solvents. Parts of chlorophe- nols were released to the natural environment during the usage. As a result, many water sources were con- taminated with CPs[1,2]. Furthermore, they also can be formed during the disinfection of phenol containing water by chlorination. Several CPs are recognized as the priority pollutants by the United States EPA (En- vironmenta…     

Photocatalysed degradation of a herbicide derivative, Dinoterb, in aqueous suspension

The photocatalytic degradation of a herbicide derivative, Dinoterb (1), has been investigated in aqueous micellar solution in the presence of titanium dioxide (TiO₂) and air as a function of irradiation time under a variety of conditions using UV and HPLC analysis techniques. The degradation kinetics was studied under different conditions such as different types of TiO₂, catalyst concentration, substrate concentration and reaction pH in the presence of air. The photocatalyst Degussa P25 was found to be more efficient catalyst as compared to other photocatalysts tested. The model compound was found to degrade more efficiently under neutral pH as compared to acidic and alkaline pH. GC/MS analysis of the irradiated samples indicate the formation of 2-isopropyl-4,6-dinitro-phenol as by-product which has been characterized on the basis of molecular ion and mass fragmentation pattern. A probable pathway for its formation has been proposed.     

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.     

Chlorophyll-sensitized phenolic resins for the photocatalytic degradation of methylene blue and synthetic blue wastewater

Journal of Sol-Gel Science and Technology - A novel method was proposed to incorporate chlorophyll molecules into the phenolic resins for the photocatalytic degradation of methylene blue and...     

Efficient removal of cadmium and 2-chlorophenol in aqueous systems by natural clay: Adsorption and photo-Fenton degradation processes

Adsorption and photo-Fenton processes were used as handy tools to ascertain the capability of natural clays to remove cadmium (Cd) and 2-chlorophenol (2-CP) from aqueous solution. Natural Fe-rich clay collected from Tejera-Esghira in Medenine area, south Tunisia, was used as a catalyst in the heterogeneous photo-Fenton oxidation of 2-CP in aqueous solution. Clay samples were acid activated to improve their adsorptive capacity for the removal of Cd. Experimental results indicated that the adsorption of Cd ions onto natural red clay of Tejera-Esghira followed the pseudo-second-order kinetic model. Langmuir model was found to describe the equilibrium data with the calculated maximum adsorption capacity of 23.59 mg g^?1 for acid-activated clay. Photo-Fenton experiments proved high activity of the natural clay catalyst, which was able to completely degrade the phenol present in the treated solution after 30 min and in the presence of ultraviolet light C (UV-C). Total organic carbon and gas chromatography analysis confirmed a 2-CP degradation mechanism toward an almost complete mineralization of the organic compound.     

Blue dye degradation in an aqueous medium by a combined photocatalytic and bacterial biodegradation process

This paper aimed at implementing a treatment system for polluted water with textile dyes, starting with a photocatalytic decomposition process using sunlight as a source of energy and continuing with a bacterial biodegradation process, in order to reach degradation percentages higher than those obtained using only one of the processes mentioned above. When water treatment with the dye in the combined system was over, an acute ecotoxicity test was performed to make sure that toxic metabolites were not produced due to biodegradation. Solophenyl Blue azoic dye, and Erionyl Blue and Terasil Blue anthraquinone dye-colored solutions were treated with the Pd/Al ₈₀ Ce ₁₀ Zr ₁₀ catalyst in a solar collector for the photocatalytic process. On the other hand, the waste dye, which was obtained from photocatalysis with a bacterial consortium from polluted areas by metals and hydrocarbons in aerobic conditions, was inoculated for biodegradation. Biodegradation was obtained for the dyes after both processes as 90.91% for the Solophenyl Blue azoic dye, and 87.80% and 87.94%, respectively, for the Erionyl Blue and Terasil Blue anthraquinone dyes. After the degradation processes, it was proven, via an ecotoxicity test with Daphnia magna , that toxic metabolites had not been produced.     

The effect of Pt oxidation state and concentration on the photocatalytic removal of aqueous ammonia with Pt-modified titania

Platinum-modified titanium (IV) oxide (Pt-TiO₂) was used to photocatalytically oxidize aqueous ammonia selectively to nitrogen gas. The photocatalyst was solvent deposited on acrylic (PMMA) supports for use in simple distributive reactors. Pt was photodeposited on the titania surface within each reactor with concentrations ranging from 0.4% (w/w) to 5.1% (w/w) Pt. The oxidation state of the deposited Pt was subsequently modified using reduced phosphotungstic acid. Time-dependent kinetic studies were used to demonstrate the effect of oxidation state on the photocatalytic activity of the Pt-TiO₂. It was determined that treatment with reduced phosphotungstic acid enhanced the reaction rate and selectivity to nitrogen gas of the Pt-TiO₂ photocatalysts. Most significantly, treatment of Pt-TiO₂ with reduced phosphotungstic acid shifts the optimum Pt concentration to higher Pt loadings. The reactor containing 3.2% (w/w) post-treated Pt demonstrated the most favorable combination of NH₃ degradation rate and selectivity to N₂, resulting in the removal of 28.34% total nitrogen from 1.7 L of a 45.5 ppm NH₃-N solution within 72 h.     

Wavelength-sensitive photocatalytic degradation of methyl orange in aqueous suspension over iron(III)-doped TiO2 nanopowders under UV and visible light irradiation

Well-crystallized iron(III)-doped TiO2 nanopowders with controlled Fe3+ doping concentration and uniform dopant distribution, have been synthesized with plasma oxidative pyrolysis. The photocatalytic reactivity of the synthesized TiO2 nanopowders with a mean particle size of 50-70 nm was quantified in terms of the degradation rates of methyl orange (MO) in aqueous TiO2 suspension under UV (mainly 365 and 316 nm) and visible light irradiation (mainly 405 and 436 nm). The photodecomposition of MO over TiO2 nanopowders followed a distinct two-stage pseudo first order kinetics. Interestingly, the photocatalytic reactivity depends not only on the iron doping concentration but also on the wavelength of the irradiating light. Under UV irradiation, nominally undoped TiO2 had much higher reactivity than Fe3+ -doped TiO2, suggesting that Fe3+ doping (> 0.05 at. %) in TiO2 with a mean particle size of approximately 60 nm was detrimental to the photocatalytic decomposition of methyl orange. Whereas, under visible light irradiation, the Fe3+ -doped TiO2 with an intermediate iron doping concentration of approximately 1 at. % had the highest photocatalytic reactivity due to the narrowing of band gap so that it could effectively absorb the light with longer wavelength. A strategy for improving the photocatalytic reactivity of Fe3+ -doped TiO2 used in the visible light region is also proposed.     

TiO2- and BaTiO3-assisted photocatalytic degradation of selected chloroorganic compounds in aqueous medium: correlation of reactivity/orientation effects of substituent groups of the pollutant molecule on the degradation rate

Investigation of the photocatalytic activity of BaTiO(3), a perovskite wideband gap semiconductor has been done in comparison with a widely used photocatalyst TiO(2) for the degradation of 4-chlorophenol (4-CP), 4-chloroaniline (4-CA), 3,4-dichloronitrobenzene (3,4-DCNB), and 2,4,5-trichlorophenol (2,4,5-TCP). BaTiO(3)/TiO(2) nanoparticles were prepared by gel-to-crystalline conversion method. BaTiO(3) has exhibited better catalytic efficiency and process efficiency compared with TiO(2) in most of the cases. The present research focuses mainly on two aspects: first the photocatalytic activity of BaTiO(3), as there are very few reports in the literature, and second the reactivity/orientation effects of substituent groups of the pollutant molecules on the degradation rate. The above chloroorganic compounds have at least one chlorine substituent in common, along with other functional groups such as -OH, -NH(2), and -NO(2). Furthermore, the effect of electron acceptors and pH on the rate of degradation is presented. The reactions follow first-order kinetics. The degradation reaction was followed by UV-vis, IR, and GC-MS spectroscopic techniques. On the basis of the identification of the intermediates, a probable degradation reaction mechanism has been proposed for each compound.     

Ozonation of activated carbons: Effect on the adsorption of selected phenolic compounds from aqueous solutions

The impact of ozonation on textural and chemical surface characteristics of two granular activated carbons (GAC), namely F400 and AQ40, and their ability to adsorb phenol (P), p-nitrophenol (PNP), and p-chlorophenol (PCP) from aqueous solutions have been studied. The porous structure of the ozone-treated carbons remained practically unchanged with regard to the virgin GAC. However, important modifications of the chemical surface and hydrophobicity were observed from FTIR spectroscopy, pH titrations, and determination of pH(PZC). As a rule, the ozone treatment at either room temperature (i.e., about 25 degrees C) or 100 degrees C gave rise to acidic surface oxygen groups (SOG). At 25 degrees C primarily carboxylic acids were formed while a more homogeneous distribution of carboxylic, lactonic, hydroxyl, and carbonyl groups was obtained at 100 degrees C. The experimental isotherms for phenolic compounds on both GAC were analyzed using the Langmuir model. Dispersive interactions between pi electrons of the ring of the aromatics and those of the carbon basal planes were thought to be the primary forces responsible for the physical adsorption whereas oxidative coupling of phenolic compounds catalyzed by basic SOG was a major cause of irreversible adsorption. The exposure of both GAC to ozone at room temperature decreased their ability to adsorb P, PNP, and PCP. However, when ozone was applied at 100 degrees C adsorption was not prevented but in some cases (P and PNP on F400) the adsorption process was even enhanced.     

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 %.     

Kinetic deoxyribose degradation assay and its application in assessing the antioxidant activities of phenolic compounds in a Fenton-type reaction system

Pro-oxidant properties of phenolic antioxidants, which are derived from their iron recycling reactivity, render the traditional deoxyribose degradation assay invalid to assess the hydroxyl radical-scavenging activity in Fenton-type reaction systems. In the present paper, we studied in detail the interactions between iron and phenolic compounds, and established a kinetic deoxyribose method by taking advantage of the distinct difference between the completion time of Fenton reaction and that of the iron-reducing process. With the newly established kinetic method, we investigated the effects of phenolics on hydroxyl radical formation in a Fenton-type system and determined successfully the second rate constants of hydroxyl radical-scavenging reactions. The site-specific and non-site-specific hydroxyl radical-scavenging ability suggested that both direct hydroxyl radical-scavenging potency and iron-chelating capacity accounted for their inhibitory effects on deoxyribose oxidation degradation. This method, more simple, time saving, and applicative than the traditional deoxyribose assay, produces as accurate results (RSD<0.05, with dynamic range from 7.5 to 575 μM) as typical methods, such as radiolysis technology, and may be of significance in evaluating and screen the hydroxyl radical-scavenging antioxidants.     

Role of water and carbonates in photocatalytic transformation of CO2 to CH4 on titania

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (?)OH radicals (oxidation product) from water, and CO(3)(-) radical anions (oxidation product) from carbonates, was detected in CO(2)-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (?)OCH(3), and methyl, (?)CH(3), radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO(2) on the surface of TiO(2) is supported by the results of first-principles calculations.