Photocatalytic degradation of p-chlorophenol by hybrid H2O2 and TiO2 in aqueous suspensions under UV irradiation.

In this study, TiO2 particles were used as photocatalysts for the degradation of aqueous p-chlorophenol (p-CP) under UV irradiation. The effect of TiO2 dose (0-3 g/L), initial p-CP concentration, H2O2 concentration (2-45 mM), solution pH (4.6-9.5), and UV light intensity on the degradation of p-CP were examined. Four oxidative degradation processes, which utilized UV alone (direct photolysis), H2O2/UV, TiO2/UV, and H2O2/TiO2/UV, were compared in a batch photoreactor with a 100-W high-pressure mercury lamp. The photodegradation of p-CP could be described by the pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. Moreover, the apparent degradation rate constants increased considerably from 3.5 × 10(-)(3) min(-)(1) (direct photolysis) to 19.9 × 10(-)(3) min(-)(1) (H2O2/TiO2/UV system).

Characterization and evaluation of the efficiency of SiO2/tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc nanocomposite as photosensitizers for oxidation of 2,4,6-trichlorophenol.

A photosensitizer tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc [ZnPc(OAr)4] was successfully encapsulated in SiO2 nanoparticle by the microemulsion method. The photosensitized composite nanoparticle was able to degrade 2,4,6-trichlorophenol (TCP) in aqueous solution. Under visible light irradiation, the nanoparticles efficiently generated reactive oxygen species; 95.4% of TCP was degraded after 270 min of reaction. Some aromatic compounds and aliphatic carboxylic acids were detected by mass spectrometry as the reaction intermediates. The results were different from those of previously reported photocatalytic reactions, in which valence band holes or hydroxyl radicals functioned as the main oxidants. The photosensitizing composite nanoparticle is potentially applicable to the oxidation of phenol.

Arsenite oxidation-enhanced photocatalytic degradation of phenolic pollutants on platinized TiO2.

The effect of As(III) on the photocatalytic degradation of phenolic pollutants such as 4-chlorophenol (4-CP) and bisphenol A (BPA) in a suspension of platinized TiO2 (Pt/TiO2) was investigated. In the presence of As(III), the photocatalytic degradation of 4-CP and BPA was significantly enhanced, and the simultaneous oxidation of As(III) to As(V) was also achieved. This positive effect of As(III) on the degradation of phenolic pollutants is attributed to the adsorption of As(V) (generated from As(III) oxidation) on the surface of Pt/TiO2, which facilitates the production of free OH radicals ((•)OHf) that are more reactive than surface-bound OH radicals ((•)OHs) toward phenolic pollutants. The generation of (•)OHf was indirectly verified by using coumarin as an OH radical trapper and comparing the yields of coumarin--OH adduct (i.e., 7-hydroxycoumarin) formed in the absence and presence of As(V). In repeated cycles of 4-CP degradation, the degradation efficiency of 4-CP gradually decreased in the absence of As(III), whereas it was mostly maintained in the presence of As(III), which was either initially present or repeatedly injected at the beginning of each cycle. The positive effect of As(III) on 4-CP degradation was observed over a wide range of As(III) concentrations (up to mM levels) with Pt/TiO2. However, a high concentration of As(III) (hundreds of µM) inhibited the degradation of 4-CP with bare TiO2. Therefore, Pt/TiO2 can be proposed as a practical photocatalyst for the simultaneous oxidation of phenolic pollutants and As(III) in industrial wastewaters.

Photolytic degradation of chlorophenols from industrial wastewaters by organic oxidants peroxy acetic acid, para nitro benzoic acid and methyl ethyl ketone peroxide: identification of reaction products.

In this investigation, chlorophenol (CP) containing industrial wastewater was remediated by ultraviolet irradiation in conjunction with organic oxidants, peroxy acetic acid (PAA); para nitro benzoic acid (PNBA); and methyl ethyl ketone peroxide (MEKP). CP mineralization was studied with regard to chemical oxygen demand (COD) and chloride ion release under identical test conditions. COD depletion to the extent of 81% by PAA, 66% by PNBA, and 67% by MEKP was noted along with an upwardly mobile trend of chloride ion release upon irradiation of samples at 254 nm. A 90-99% decrease in CP concentration (as per high pressure liquid chromatography (HPLC) analysis) was achieved with an additional 15.0 ml of organic oxidant in all cases. Gas chromatography high resolution mass spectroscopy (GC-HRMS) results also indicated the formation of such reaction products as are free from chlorine substitutions. This treatment also leads to total decolorization of the collected samples.

N-TiO2/gamma-Al2O3 granules: preparation, characterization and photocatalytic activity for the degradation of 2,4-dichlorophenol.

Nitrogen doping TiO2 and gamma-Al2O3 composite oxide granules (N-TiO2/gamma-Al2O3) were prepared by co-precipitation/oil-drop/calcination in gaseous NH3 process using titanium sulphate and aluminum nitrate as raw materials. After calcination at 550 degrees C in NH3 atmosphere, the composite granules showed anatase TiO2 and gamma-Al2O3 phases with the granularity of 0.5-1.0 mm. The anatase crystallite size of composite granules was range from 3.5-25 nm calculated from XRD result. The UV-Vis spectra and N 1s XPS spectra indicated that N atoms were incorporated into the TiO2 crystal lattice. The product granules could be used as a photocatalyst in moving bed reactor, and was demonstrated a higher visible-light photocatalytic activity for 2,4-dichlorophenol degradation compared with commercial P25 TiO2. When the mole ratio of TiO2 to Al2O3 equal to 1.0 showed the highest catalytic activity, the degradation percentage of 2,4-chlorophenol could be up to 92.5%, under 60 W fluorescent light irradiation for 9 hours. The high visible-light photocatalytic activity might be a synergetic effect of nitrogen doping and the form of binary metal oxide of TiO2 and gamma-Al2O3.

Investigation of UV-assisted chlorophenol congeners' degradation by organic oxidant p-nitrobenzoic acid in basic media.

This research specifically addressed the photodegradation of selected model chlorophenol (CP) congeners, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), by an organic oxidant, p-nitrobenzoic acid (PNBA), in basic media. The reactions were followed by high-pressure liquid chromatography and gas chromatography-mass spectroscopy analysis for residual concentration and the identification of photodegraded products respectively. Initial degradation was confirmed by the formation of ring cleavage compounds, and subsequent mineralization was evidently marked by an increase in release of chloride ions in the time course profile. The presence of fewer/no chlorine atoms in the degraded compounds corroborated the mineralization by UV/PNBA action. The chemical oxygen demand (COD) was also observed to fall appreciably to the extent of 73% during all CP congeners' degradation. The maximum COD decrease was observed in PNBA-assisted 4-CP degradation. The overall degradation kinetics conforming to second-order reaction is observed to follow the order 4-CP > 2,4,6-TCP ∼ PCP ∼ 2,4-DCP. The findings of this investigation elucidated the fact that PNBA was capable of successfully degrading/mineralizing the selected CP congeners.

Photochemical degradation of 4-chlorophenol in the aqueous phase using peroxyacetic acid (PAA).

The photochemical degradation of 4-chlorophenol (4-CP) using ultraviolet irradiation (UV) of 6, 12 and 18 W with peroxyacetic acid (PAA) was studied in a batch reactor. The objective of this work was to investigate degradation and mineralization of 4-CP by PAA. The degradation efficiency increased with increasing UV input. The degradation process was also pH and initial PAA concentration dependent. The optimum conditions for the photochemical degradation of 4-CP as UV input, pH and PAA concentration was found to be 18 W, 9.5 and 3,040 ppm. The reaction efficiency decreased with increasing initial 4-CP concentrations. More than 95% mineralization of 4-CP was achieved with the UV/PAA process. The chloride ion concentration and chemical oxygen demand (COD) was evaluated. The chloride ion concentration and COD were decreased gradually with increasing UV input. Samples were analyzed by high pressure liquid chromatography (HPLC), UV spectrophotometry and gas chromatography-mass spectrometry (GC-MS) for residual concentration and identification of final degraded products.

Environmental implications and applications of carbon nanomaterials in water treatment.

Carbon nanomaterials have been proposed as a basis for developing new technologies for photocatalytic oxidation and disinfection, improved membrane processes, adsorbents, and biofilm-resistant surfaces. This study details recent progress towards the development of these proposed applications. We explored the use of carbon nanomaterials such as fullerene C60, single-wall carbon nanotubes (SWCNTs), and multi-wall carbon nanotubes (MWCNTs) for a range of new technologies including, degradation of a probe organic compound by in situ generation of reactive oxygen species (ROS), new strategies for microbial disinfection, and the inhibition of biofilm development on membrane surfaces. The results show that the degradation of 2-chlorophenol by ROS produced microbial inactivation, and the mobility of the nanoparticle aggregates of the carbon nanomaterials all increased as suspensions were fractionated to enrich with smaller aggregates with sonication followed by successive membrane filtration.

Synthesis of indium borate and its application in photodegradation of 4-chlorophenol.

Indium borate has been prepared by a sol-gel method. The structure, morphology, and photophysics of the resultant photocatalysts have been studied via the techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and diffuse reflectance UV-visible light spectroscopy. These photocatalysts have been used to photodegrade 4-chlorophenol. The photocatalytic activity depends on the annealing temperature during preparation. It is found that borates can exhibit a high photodegradation activity under UV-light irradiation, for which the efficiency can be higher than that of as-prepared TiO(2). This is explained according to the results of fluorescence spectra and valence band X-ray photoelectron spectroscopy (XPS). It is confirmed by the results of time-resolved photoluminescence decay spectra; i.e., the lifetime of electrons and holes involved in the radiative process can be longer for the borates than that for TiO(2). This implies that indium borate can be a promising photocatalyst for future applications in treatment of environment contaminants.

Mineralization of p-chlorophenol in water solution by AOPs based on UV irradiation.

Protection of clean aquifers requires radical minimization of water consumption, overall reduction of wastewater and, furthermore, minimization of wastewater loading. Many organic pollutants in wastewater present a specific problem because of their toxicity, bioaccumulation and poor biodegradability. The scope of this paper is to investigate and identify the benefits offered by advanced oxidation processes (AOPs) as destructive methods for treatment of wastewater loaded with recalcitrant organic pollutants. The study was performed on model wastewater containing p-chlorophenol as a representative of organic chemical industry intermediates. Several UV based AOPs were studied: UV, UV/H2O2, UV/O3, UV/H2O2/O3 and UV/Fenton. Optimal process conditions for the highest mineralization efficiency in the investigated range (pH, [H2O2] and [Fe2+]) have been determined on the basis of HPLC measurements and the following ecological parameters: total organic carbon (TOC), adsorbable organic halides (AOX), chemical oxygen demand (COD) and biochemical oxygen demand (BOD5). Toxicity is one of the most important ecological parameters in determining the level of water pollution. In this study, toxicity tests were performed on the zooplankton Daphnia magna in order to evaluate efficiency of the applied treatments. The UV/ Fenton and UV/H2O2/O3 processes were found to be the most appropriate processes for degradation and mineralization of p-chlorophenol. Complete degradation was achieved after 15 minutes ofUV/Fenton process treatment, while 92.1% TOC and 98.3% AOX removals were obtained after treatment of 60 minutes.

Physical insight into the sonochemical degradation of 2,4-dichlorophenol.

In this study, we have attempted to reveal the physical or mechanistic features of the sonochemical degradation of 2,4-dichlorophenol (2,4-DCP). The principal physical phenomenon underlying sonochemical effects is radial motion of cavitation bubbles and production of radicals from transient collapse of these bubbles. We reveal some important physical facets of sonochemical degradation of 2,4-DCP by adopting dual approach of coupling experimental results with simulations of radial motion of cavitation bubble. First, the location of the degradation is predominantly the interfacial region between bubble and bulk medium, and secondly, the extent of degradation is controlled by conservation--and not the production--of oxidizing radicals that affects the probability of radical-pollutant interaction.

Radiolytic oxidation and degradation of 2,4-dichlorophenol in aqueous solutions.

Radiolytic oxidation of 2,4-dichlorophenol (2,4-DClP) in aqueous solutions demonstrated that ·OH predominantly adds to the unsubstituted positions of the aromatic ring and that elimination of chloride at the 4 position is important because the -OH group enhances the electron density at this position, which is favorable for the electrophilic reactions. The total yield obtained was 0.540 µmol/J. Radiation-induced degradation of 2,4-DClP was conducted in oxygen-free aqueous solutions (0.1, 0.25, 0.50, and 0.7 mmol/dm3), saturated with N2O, and aerated and under irradiation at low and high doses. The results demonstrate that the largest degradation occurred in oxygen-free solutions due to oxidation (·OH) and reduction reactions (H· and [Formula: see text]) and attack of the [Formula: see text] at the ipso position of -Cl, producing HCl. The degradation was affected to a large extent by the concentration and to a lesser extent by the presence or absence of oxygen in which the 2,4-DClP solution was irradiated. At concentrations less than 1 mmol/dm3, 2,4-DClP was degraded in the solution at an absorbed dose level of 1 kGy. At higher doses, the product concentrations increased to up to 30% of the dose required for the total degradation of 2,4-DClP; then, they decreased. A graph plotting the logarithm of the relative concentration as a function of the dose shows a linear correlation, which indicates that the radiolytic degradation followed pseudo-first-order reaction kinetics. The oxidation was followed by the chemical oxygen demand (COD). COD decreases when the solute concentration increases. This fact has a dependence on the presence or absence of oxygen too.

Synthesis of graphene/black phosphorus hybrid with highly stable P-C bond towards the enhancement of photocatalytic activity.

Black phosphorus (BP), a superior two-dimensional (2D) semiconductor, has attracted much attention due to its unique properties. The graphene (GR)-BP hybrid was synthesized through one pot chemical vapor transport (CVT) approach. The characterization results indicated that P atom was successfully incorporated into GR by the formation of P-C bond. Remarkably, the newly-synthesized GR-BP represented high photocatalytic activity towards 2-chlorophenol (2-CP) degradation, due to the high efficiency of charge separation and transformation caused by the direct band gap of BP and carrier mobility of GR. The removal efficiency for 2-CP reached up to 87.08% within visible light irradiation for 180 min (λ > 420 nm). The degradation rate of GR-BP hybrid for 2-CP was approximately 7.29-fold than that of BP within 30 min. In addition, the little increasing of the peak for P-O bond in GR-BP hybrid was observed after being exposed in air for 15 days, meant that the stability of BP was significantly enhanced. It was caused by the decreasing of the oxidation sites in BP due to the formation of P-C bond in hybrid. In brief, our synthetic method for GR-BP not only provides a novel route for the improvement of the stability of BP, but also constitutes an insight into the promising practical application of BP in the photocatalysis field.

Interactive Fe2O3/porous SiO2 nanospheres for photocatalytic degradation of organic pollutants: Kinetic and mechanistic approach.

A uniformly distributed mesoporous silica nanospheres has been successfully synthesized. Silica nanospheres have been loaded with different content of Fe2O3 nanoparticles synthesized by the sol-gel process followed by calcination to form the Fe2O3 supported on silica nanospheres composite. The as-synthesized photocatalyst has been characterized for crystal structure, morphology, stability, surface area and also surface composition was determined. The photocatalytic oxidation ability of the composite photocatalyst was evaluated by degrading aqueous solutions of Methylene Blue and Congo red dyes under visible light having intense absorption in the wavelength range between 550 and 560 nm. The prime significance of silica is to act as catalyst support for uniform distribution of hematite particles for enhanced catalytic reactivity. Highest degradation has been achieved with 20 wt % loading of hematite nanoparticles indicating the less agglomeration and availability of more catalytic sites. Furthermore, colorless organic pollutants 2-chlorophenol and 2, 4-dichlorophenol have been degraded with high efficiency in the presence of H2O2 oxidizer. The scavenger experiments confirmed that hydroxyl radicals are the majorly participating species in this catalytic system. The composite system also shows good recyclability of the materials and advocates the promising nature of the designed system for multiple hazardous environmental contaminants.

Theoretical analysis of sonochemical degradation of phenol and its chloro-derivatives.

Phenol and its chloro-derivatives contribute significantly to environmental pollution hazards due to their high degree of toxicity as well as improper disposal methods. Cavitation can be used successfully for degradation of phenolic compounds and the rates of degradation are dependent on the type of the primary pollutant in the system. In the present work, a theoretical explanation has been provided to explain the observed degradation trends of phenol and chlorophenols on the basis of concentration of the pollutant at the cavitation bubble/solution interface. Chemical stability of these compounds towards radical attack in the liquid phase has been discussed. It has been observed that chloro-derivates degrade much faster as compared to the parent compound due to higher hydrophobicity of chloro-derivates.

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media.

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.

Degradation of 4-chlorophenol in TiO2, WO3, SnO2, TiO2/WO3 and TiO2/SnO2 systems.

The present study was undertaken to evaluate the degradation performance of 4-chlorophenol (4-CP) using TiO2/WO3 and TiO2/SnO2 systems. A BET surface area analyzer, UV-vis spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and electron spectroscopy for chemical analysis (ESCA) were employed to characterize the photocatalyst. The band edge wavelength increased to 475 nm and gap energy decreased to 2.61 eV in the TiO2/WO3 system as compare to the single TiO2. Although the specific surfaces area of TiO2/WO3 decreases due to its larger size as compared to either TiO2 or WO3, the 4-CP degradation efficiency significantly increased as compared to single TiO2 or WO3 system at 435 nm wavelength. The TiO2/WO3 degradation of 4-CP at 369 nm was in fact inhibited. For TiO2/SnO2, the degradation efficiency also suffered at 369 nm, and only slightly increased compared to otherwise hardly 4-CP degraded in single TiO2 or SnO2 system. Since there is a significant accumulation of byproducts, the buildup of these intermediates on the catalyst surface may be responsible for their poor performance.

Photochemical treatment of 2-chlorophenol aqueous solutions using ultraviolet radiation, hydrogen peroxide and photo-Fenton reaction.

In the present work, the photochemical oxidation of 2-chlorophenol aqueous solutions in a batch recycle photochemical reactor using ultraviolet irradiation and hydrogen peroxide was studied. Specifically, the effect of hydrogen peroxide initial concentration (0-10316 mg L(-1)) and 2-chlorophenol initial concentration (150-3000 mg L(-1)) was examined. The process was attended via total organic carbon (TOC), 2-chlorophenol, chloride ion, acetic acid, formic acid and pH measurements. The conversion of 2-chlorophenol observed was always much higher than the corresponding total organic carbon removal, whereas the increase in hydrogen peroxide amount in the solution led to higher values of 2-chlorophenol conversion and total organic carbon removal. Finally, the photo-Fenton reaction was applied to the oxidation of 2-chlorophenol, leading to a higher degree of mineralization of the parent compound.

Photodegradation of 2,4-dichlorophenol by supported Pd(X2) catalyst (X = Cl, Br, N3): a HOMO manipulating point of view.

Three different palladium(II) complexes with ligands containing nitrogenized aromatic rings were investigated theoretically as model to obtain the computational band gap energies. The results demonstrated promising possibility for designing palladium(II) complexes with photocatalytic properties at visible light irradiation. Deliberated products were synthesized via grafting on the silica-coated Fe3O4 magnetic nanoparticles (Fe3O4@SiO2). Formation of complexes on the surface of Fe3O4@SiO2, as insoluble and reusable photocatalysts, was proved by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), transmission electron microscope (TEM), and scanning electron microscopy (SEM) analyses. The trend of the band gap energies of prepared structures was calculated via experimental and theoretical methods. The photocatalytic capability of these nanoparticles was investigated in degradation of 2,4-dichlorophenol by means of HPLC analysis. A tentative reaction mechanism for the formation of intermediates was proposed. Graphical abstract ᅟ.

2,4-dichlorophenol degradation by an integrated process: photoelectrocatalytic oxidation and E-Fenton oxidation.

A new reactor system was designed for an integrated process involving photoelectrocatalytic oxidation (PECO) and electro-Fenton (E-Fenton) oxidation. Its efficiency was evaluated in terms of 2,4-dichlorophenol (2,4-DCP) degradation in aqueous solution. In this process, a TiO2 electrode and an iron (Fe) electrode were used as anodes in parallel, while graphite felt (GF) was used as a cathode. When an electrical current is applied between the anodes and the cathode, the iron anode can release Fe2+ and the GF cathode can generate H2O2 continuously in the reaction solution. Under UV-A illumination, while a H2O2-assisted PECO reaction occurs on the surface of the TiO2 photo anode, an E-Fenton reaction takes place in the solution. The experimental results demonstrated that 2,4-DCP degradation in aqueous solution was greatly enhanced because of the interaction between the two types of reactions. Moreover, the effect of pH as an important factor was investigated. It was found that the combined reaction becomes less pH sensitive than the typical E-Fenton reaction and may be suitable for application in a wide pH range.