Preparation and characterization of Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst for degradation dye wastewater

In order to develop a catalyst with high activity for catalytic wet oxidation （CWO） process at room temperature and atmospheric pressure, Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst was prepared by consecutive impregnation method and the prepared parameters were optimized. The structure of the catalyst was characterized by BET, XRF, SEM and XPS technologies, and the actual wastewater was used to investigate the catalytic activity of Fe2O3-CeO2-TiO2/γ-Al2O3 in CWO process. The experimental results showed that the prepared catalyst exhibited good catalytic activity when the doping amount of Ti was 1.0 wt% （the weight ratio of Ti to carriers）, and the middle product, Fe2O3-CeO2-TiO2/γ-Al2O3, was calcined in 450℃ for 2 h. The CWO experiment for treating actual dye wastewater indicated that the COD, color and TOC of actual wastewater were decreased by 62.23%, 50.12% and 41.26% in 3 h, respectively, and the ratio of BOD5/COD was increased from 0.19 to 0.30.     

A novel graphene oxide-carbon nanotubes anchored α-FeOOH hybrid activated persulfate system for enhanced degradation of Orange II

Persulfate activation has been applied as one of the efficient advanced oxidation processes(AOPs) to remediate polluted environments. In this study, a novel α-FeOOH anchored by graphene oxide(GO)-carbon nanotubes(CNTs) aerogel(α-FeOOH@GCA) nanocomposite activated persulfate system(α-FeOOH@GCA + K_2S_2O_8) was applied for decolorization of Orange Ⅱ(OⅡ). The decolorization of OⅡ was remarkably enhanced to a level of ～ 99% in this system compared with that of pristine α-FeOOH(～ 44%) or GO-CNTs(～18%). The enhanced catalytic activity of α-FeOOH@GCA was due to the formation of a heterojunction byα-FeOOH and GO-CNTs as confirmed by the presence of Fe–O–C chemical bonds. The degradation intermediates of OⅡ were comprehensively identified. The proposed degradation pathway of OⅡ begins with the destruction of the conjugated structures of OⅡ by the dominant reactive oxygen species, surface-bound SO_4~(·-). The decolorization efficiency of OⅡ by the α-FeOOH@GCA activated persulfate system decreased from the first to third cycle of recycling. Ultraviolet(UV) irradiation or introduction of a small amount of Fe~(2+) could restore the activation of this system. The results show that the α-FeOOH@GCA persulfate activation system promises to be a highly efficient environmental remediation method for organic pollutants.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

Electrically enhanced photodegradation of an azodye(Acid Orange Ⅱ) using a Pt/TiO2 film electrode irradiating with an UV lamp

A photoelectrochemical process in the degradation of an azodye(Acid Orange II)on a Pt/TiO2 film electrode was investigated.By using the glass device and the voltage stabilized source of direct current,decolorization ratios higher than 78% were observed during a period of 5h.Comparing this value with the sum of the decolorization ratios obtained by a sole application of electrochemical(lower than 3%)and photochemical(about 23%)procedures, a significant synergic effect between both processes was observed.The effects of adscititious voltage and pH value on the decolorization ratios were obvious while the effect of the amount of aeration was minor.     

Degradation of Reactive Yellow 86 with photo-Fenton process driven by solar light

The decolorization of Reactive Yellow 86(RY 86),one of reactive azo dyes,was investigated in the presence of Fenton reagent under solar light irradiation.The decolorization rate was strongly influenced by pH,initial concentrations of H 2 O 2 and Fe(II),and so on.An initial concentration of 40 mg/L was decolored more than 90% after 20 min under optimum conditions.The activation energy of the solar photo-Fenton reaction was 1.50 kJ/mol for RY 86 in the temperature range of 10-60°C.In the kinetic study,the rate constant of RY 86 with OH· radicals could be estimated to be 1.7 × 10 10 L/(mol·sec).The decolorization efficiency of RY 86 under solar light irradiation was comparable to the artificial light irradiation.The decrease of TOC as a result of mineralization of RY 86 was observed during photo-Fenton process.The rate of RY 86 mineralization was about 83% under UV irradiation after 24 hr.The formation of chloride,sulfate,nitrate and ammonium ions as end-products was observed during the photocatalytic process.The decomposition of RY 86 gave two kinds of intermediate products.The degradation mechanism of RY 86 was proposed on the base of the identified intermediates.     

Photocatalytic remediation of γ-HCH contaminated soil induced by α-Fe2O3 and TiO2

Heterogeneous photocatalytic degradation of γ-HCH on soil surfaces was carded out to evaluate the photocatalytic effectiveness of α-Fe2O3 and TiO2 toward degrading γ-HCH on soil surfaces. After being spiked with γ-HCH, soil samples were loaded with α-Fe2O3 or TiO2 and exposed to UV-light irradiation. Different catalyst loads, 0%, 2%, 5%, 7%, and 10% (wt.)α-Fe2O3 ; 0%, 0.5%, 1%, 2:(Wt.)TiO2, were tested for up to 7 d irradiation. The effects of soil thickness, acidity, and humic substances were also investigated. The obtained results indicated that the γ-HCH photodegradation follows the pseudo-first-order kinetics. The addition of α-Fe2O3 or TiO2 accelerates the photodegradation of γ-HCH, while the photodegradation rate decreases when the content of α-Fe2O3 exceeds 7% (wt.).The degradation rate increases with the soil pH value. Humic substances inhibit the photocatalytic degradation of γ-HCH., and trichlorobenzene are detected as photodegradation intermediates, which are gradually degraded with the photodegradation evolution.     

TiO2–PANI/Cork composite: A new floating photocatalyst for the treatment of organic pollutants under sunlight irradiation

A novel photocatalyst based on TiO_2–PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline(PANI)–modified TiO_2 on cork. The TiO_2–PANI/Cork catalyst shows the unique feature of floating on the water surface. The as-synthesized catalyst was characterized by X-ray diffraction(XRD),scanning electron micrograph(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), Fourier transform infrared spectroscopy(FT-IR), UV–vis diffuse reflectance spectra(UV–vis DRS) and the Brunauer–Emmett–Teller(BET) surface area analysis. Characterization suggested the formation of anatase highly dispersed on the cork surface. The prepared floating photocatalyst showed high efficiency for the degradation of methyl orange dye and other organic pollutants under solar irradiation and constrained conditions, i.e., no-stirring and no-oxygenation. The TiO_2–PANI/Cork floating photocatalyst can be reused for at least four consecutive times without significant decrease of the degradation efficiency.     

Photocatalytic degradation of endocrine disruptor Bisphenol-A in the presence of prepared CexZn1-xO nanocomposites under irradiation of sunlight

Photocatalytic degradation of Bisphenol A （BPA）, a representative endocrine disruptor chemical, was carried out under irradiation of sunlight in the presence of CexZn1-xO nanophotocatalyst. Cerium （Ce） ions were successfully incorporated into the bulk lattice of ZnO by simple co-precipitation process. The CexZn1-xO composite nanostructures exhibited higher photocatalytic efficiency than pure ZnO in the degradation of BPA under sunlight irradiation and nearly complete mineralization of BPA was achieved. The degradation rate was strongly dependent on factors such as the size and structure of catalyst, doping material concentration, BPA concentration, catalyst load, irradiation time and pH levels. This work suggested that the CexZn1-xO assisted photocatalytic degradation is a versatile, economic, environmentally benign and efficient method for BPA removal in the aqueous environment.     

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

The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO2 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 CO2, CI^- and NO3^-. Complete photo-oxidation of nitrogen to NO3^- occurred very slowlyvia the intermediate formation of NH4^ and NO2^- .     

Photochemical behavior of benzo[a]pyrene on soil surfaces under UV light irradiation

The rates of photodegradation and photocatalysis of benzo [a]pyrene （BaP） on soil surfaces under UV light have been studied. Different parameters such as temperature, soil particle sizes, and soil depth responsible for photodegradation, catalyst loads and wavelength of UV irradiation blamed for photocatalysis have been monitored. The results obtained indicated that BaP photodegradation follows pseudo-first-order kinetics. BaP photodegradation was the fastest at 30℃ . The rates of BaP photodegradation at different soil particle size followed the order： less than 1 mm〉less than 0.45 mm〉less than 0.25 mm. When the soil depth increased from 1 mm to 4 ram, the half-life increased from 13.23 d to 17.73 d. The additions of TiO2 or Fe2O3 accelerated the photodegradation of BaP, and the photocatalysis of BaP follows pseudo-first-order kinetics. Changes in catalyst loads of TiO2 （0.5%, 1%, 2%, and 3% （wt）） or Fe203 （2%, 5%, 7%, and 10% （wt）） did not significantly affect the degradation rates. Both BaP photocatalysis in the presence of TiO2 and Fe2O3 were the fastest at 254 nm UV irradiation.     

Photodegradation of Orange Ⅱ using waste paper sludge-derived heterogeneous catalyst in the presence of oxalate under ultraviolet light emitting diode irradiation

A waste paper sludge-derived heterogeneous catalyst(WPS-Fe-350) was synthesized via a facile method and successfully applied for the degradation of Orange Ⅱ in the presence of oxalic acid under the illumination of ultraviolet light emitting diode(UV-LED) Powder X-ray diffraction,Fourier-transform infrared spectroscopy,scanning electronic microscopy and N2 sorption isotherm analysis indicated the formation of α-Fe2O3 in the mesoporous nanocomposite.The degradation test showed that WPS-Fe-350 exhibited rapid Orange Ⅱ(OⅡ) degradation and mineralization in the presence of oxalic acid under the illumination of UV-LED.The effects of p H,oxalic acid concentration and dosage of the catalyst on the degradation of OⅡ were evaluated,respectively.Under the optimal conditions(1 g/L catalyst dosage,2 mmol/L oxalic acid and p H 3.0),the degradation percentage for a solution containing 30 mg/L OⅡ reached 83.4% under illumination by UV-LED for 80 min.Moreover,five cyclic tests for OⅡ degradation suggested that WPS-Fe-350 exhibited excellent stability of catalytic activity.Hence,this study provides an alternative environmentally friendly way to reuse waste paper sludge and an effective and economically viable method for degradation of azo dyes and other refractory organic pollutants in water.     

Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni/Fe–Fe3O4 nanocomposites

Ni/Fe-Fe_3O_4 nanocomposites were synthesized for dechlorination of 2,4-dichlorophenol(2,4-DCP). The effects of the Ni content in Ni/Fe-Fe_3O_4 nanocomposites, solution pH, and common dissolved ions on the dechlorination efficiency were investigated, in addition to the reusability of the nanocomposites. The results showed that increasing content of Ni in Ni/Fe–Fe_3O_4 nanocomposites, from 1 to 5 wt.%, greatly increased the dechlorination efficiency; the Ni/Fe–Fe_3O_4 nanocomposites had much higher dechlorination efficiency than bare Ni/Fe nanoparticles. Ni content of 5 wt.% and initial p H below 6.0 was found to be the optimal conditions for the catalytic dechlorination of 2,4-DCP. Both 2,4-DCP and the intermediate product 2-chlorophenol(2-CP) were completely removed, and the concentration of the final product phenol was close to the theoretical phenol production from complete dechlorination of 20 mg/L of 2,4-DCP, after 3 hr reaction at initial p H value of 6.0,3 g/L Ni/Fe-Fe_3O_4 , 5 wt.% Ni content in the composite, and temperature of 22℃. 2,4-DCP dechlorination was enhanced by Cl-and inhibited by NO3-and SO_4~(2-). The nanocomposites were easily separated from the solution by an applied magnetic field. When the catalyst was reused, the removal efficiency of 2,4-DCP was almost 100% for the first seven uses, and gradually decreased to 75% in cycles 8–10. Therefore, the Ni/Fe–Fe_3O_4 nanocomposites can be considered as a potentially effective tool for remediation of pollution by 2,4-DCP.     

Influence of supports on photocatalytic degradation of phenol and 4-chlorophenol in aqueous suspensions of titanium dioxide

The photocatalytic degradation of phenol and 4-chlorophenol (4-CP) in aqueous suspensions with the use of titanium dioxide (TiO2 ) under UV irradiation was examined. The effects of different supporting materials mixed physically with TiO2 were studied to achieve maximum degradation efficiency. Among the three supports, namely activated carbon (AC), silica (SiO2 ) and zeolite (ZSM-5), all exhibited paramount efficiency for degradation of phenol and 4-CP and was better than TiO2 alone. The optimum concentration was found to be 50 mg for all supporting materials. The efficiency order of the three supports was as follows: AC > ZSM-5 > SiO2 , respectively. Whilst, the degradation of phenol and 4-CP was improved from 70.6% to 87.6% and 80.6% to 89.7%, respectively, within 120 min photocatalysis in the presence of optimal amount of AC. The degradation was also comparatively enhanced in the presence of cheaper rice husk and the activity was closed to ZSM-5 and lower than AC.     

Treatment of phenol wastewater by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process

The catalyst of CuOx/Al2O3 was prepared by the dipping-sedimentation method using γ-Al2O3 as a carrier. CuO and Cu2O were loaded on the surface of γ-Al2O3, characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In the presence of CuOx/Al2O3, the microwave-induced chlorine dioxide (ClO2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol. The relationships between removal percentage and initial ClO2 concentration, catalyst dosage, microwave power, contact time, initial phenol concentration and pH were investigated and the results showed that microwave-induced ClO2-CuOx/Al2O3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage, extensive pH range. Under a given condition (ClO2 concentration 80 mg/L, microwave power 50 W, contact time 5 min, catalyst dosage 50 g/L, pH 9), phenol removal percentage approached 92.24%, corresponding to 79.13% of CODCr removal. The removal of phenol by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics. Compared with traditional ClO2 oxidation, ClO2 catalytic oxidation and microwave-induced ClO2 oxidation, microwave-induced ClO2 catalytic oxidation system could significantly enhance the degradation efficiency. It provides an effective technology for the removal of phenol wastewater.     

Reaction site and mechanism in the UV or visible light induced TiO2 photodegradation of Orange G

For TiO2 heterogeneous reaction, the reaction site and the detailed mechanism are interesting and controversy topics. In this paper, effects of surface fluorination of TiO2 on the photocatalytic degradation of an azo dye, Orange G（OG） under UV or visible light irradiation were investigated, and the possible reaction site and mechanism were elucidated. The adsorption of OG on TiO2 was nearly inhibited by fluoride but its UV light induced photodegradation rate was greatly increased by a factor of about 2.7, which was due to the more generated free hydroxyl radicals. It supported the views that fluoride could desorb the oxidant species from surface and that the reaction sites could move to the bulk solution. In TiO2/Vis system, the observed inhibition effects of fluorination could be interpreted by the competitive adsorption, which provided additional evidences that the visible light sensitized photodegradation of dye pollutants on the catalyst surface.     

Decontamination of alachlor herbicide wastewater by a continuous dosing mode ultrasound/Fe2+/H2O2 process

We used a ultrasound/Fe2+/H2O2 process in continuous dosing mode to degrade the alachlor.Experimental results indicated that lower pH levels enhanced the degradation and mineralization of alachlor. The maximum alachlor degradation(initial alachlor concentration of 50 mg/L) was as high as 100% at pH 3 with ultrasound of 100 Watts, 20 mg/L of Fe2+, 2 mg/min of H2O2 and 20℃ within60 min reaction combined with 46.8% total organic carbon removal. Higher reaction temperatures inhibited the degradation of alachlor. Adequate dosages of Fe2+and H2O2 in ultrasound/Fe2+/H2O2process not only enhance the degradation efficiency of alachlor but also save the operational cost than the sole ultrasound or Fenton process. A continuous dosing mode ultrasound/Fe2+/H2O2 process was proven as an effective method to degrade the alachlor.     

Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of Acid Orange 7 in water

Bimetallic Fe-Co/GAC （granular activated carbon） was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate （PS, S2O8 2-） process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 （AO7） was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles.     

Photochemically enhanced degradation of phenol using heterogeneous Fenton-type catalysts

The degradation of phenol was carriced out using heterogeneous Fenton-type catalysts in the presence of H2O2 and UV.Catalysts were prepared by exchanging and immobilizing Fe^2 in zeolite 13X,silica gel or Al2O3.The concentration of phenol solution was 100mg/L.The amount of H2O2 added was the stoichiometric amount of H2O2 required for the total oxidation of phenol.Under the irradiation of medium pressure light(300W)phenol was mineralized within 1 h in the presence of Fe^2 /zeolite 13X.The COD removal rate was enhanced in the presence of Fe^2 /zeolite 13X compared to that of Fe^2 /silica gel of Fe^2 /Al2O3.Analogous homogenous photo-Fenton reaction with equivalent Fe^2 was also carried out to evaluate the catalysis efficiency of Fe^2 /zeolite 13X.Results showed that the COD removal rate was near to that of homogeneous Fenton,while heterogeneous Fe^2 /zeolite 13X catalyst coule be recycled.     

Photo-induced transformations of Hg(Ⅱ) species in the presence of Nitzschia hantzschiana,ferric ion,and humic acid

Effects of algae Nitzschia hantzschiana, Fe(Ⅲ) ions, humic acid, and pH on the photochemical reduction of Hg(Ⅱ) using the irradiation of metal halide lamps (λ 365 nm, 250 W) were investigated. The photoreduction rate of Hg(Ⅱ) was found to increase with increasing concentrations of algae, Fe(Ⅲ) ions, and humic acid. Alteration of pH value affected the photoreduction of Hg(Ⅱ) in aqueous solution with or without algae. The photoreduction rate of Hg(II) decreased with increasing initial Hg(Ⅱ) concentration in aqueous solution in the presence of algae. The photochemical kinetics of initial Hg(Ⅱ) and algae concentrations on the photoreduction of Hg(Ⅱ) were studied at pH 7.0. The study on the total Hg mass balance in terms of photochemical process revealed that more than 42% of Hg(Ⅱ) from the algal suspension was reduced to volatile metallic Hg under the conditions investigated.     

Treatment of phenol wastewater by microwave-induced CIO_2-CuO_x/Al_2O_3 catalytic oxidation process

The catalyst of CuO_x/Al_2O_3 was prepared by the dipping-sedimentation method usingγ-Al_2O_3 as a supporter.CuO and Cu_2O were loaded on the surface of Al_2O_3,characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).In the presence of CuO_x/Al_2O_3,the microwave-induced chlorine dioxide(ClO_2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol.The factors influencing phenol removal were investigated and the results showed that microwave-induced ClO_2-CuO_x/Al_2O_3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage,extensive pH range.Under a given condition(ClO_2 concentration 80 mg/L,microwave power 50 W,contact time 5 min,catalyst dosage 50 g/L,pH 9),phenol removal percentage approached 92.24%,corresponding to 79.13% of COD_(Cr) removal.The removal of phenol by microwave-induced ClO_2-CuO_x/Al_2O_3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics.Compared with traditional ClO_2 oxidation,ClO_2 catalytic oxidation and microwave-induced ClO_2 oxidation,microwave-induced ClO_2 catalytic oxidation system could significantly enhance the degradation efficiency.It provides an effective technology for the removal of phenol wastewater.