Laser-induced removal of a dye C.I. Acid Red 87 using n-type WO3 semiconductor catalyst

Water contamination by organic substances such as dyes is of great concern worldwide due to their utilization in many industrial processes and environmental concerns. To cater the needs for waste water treatment polluted with organic dyes, laser-induced photocatalytic process was investigated for removal of a dye derivative namely Acid Red 87 using n-type WO₃ semiconductor catalyst. The degradation was investigated in aqueous suspensions of tungsten oxide under different experimental conditions using laser instead of conventional UV lamp as an irradiation source. The degradation process was monitored by measuring the change in dye concentration as a function of laser irradiation time by employing UV spectroscopic analysis. The degradation of dye was studied by varying different parameters such as laser energy, reaction pH, substrate concentration, catalyst concentration, and in the presence of electron acceptors such as hydrogen peroxide (H₂O₂), and potassium bromate (KBrO₃). The degradation rates were found to be strongly dependent on all the above-mentioned parameters. Our experimental results revealed that the dye degradation process was very fast (within few minutes) under laser irradiation as compared to conventional setups using broad spectral lamps (hours or days) and this laser-induced photocatalytic degradation method could be an effective means to eliminate the pollutants present in liquid phase. The experience gained through this study could be beneficial for treatment of waste water contaminated with organic dyes and other organic pollutants.     

Decolorization of C.I. Reactive Red 2 by catalytic ozonation processes

This study adopted O3, UV/TiO2/O3, O3/Mn(II) and O3/MnO2 systems to assess the decolorization efficiency of C.I. Reactive Red 2 (RR2). The decolorization rate increased with concentrations of Mn(II) and MnO2 in the ranges 0.05-0.1 and 0.05-0.8 g/l, respectively. However, when 0.5-3g/l TiO2 was added, the effect of TiO2 dosage for RR2 decolorization was insignificant in the UV/TiO2/O3 system. At pH 2, the decolorization rate constants of O3, O3/Mn(II) (0.05 g/l), O3/Mn(II) (0.1g/l), O3/Mn(II) (0.15 g/l), O3/MnO2 (0.05 g/l) and O3/MnO2 (0.8 g/l) were 0.816, 2.001, 3.173, 3.087, 1.040 and 1.648 min(-1), respectively. After 5 min of reaction, the decolorization rates followed the order O3/Mn(II)>O3/MnO2>O3>UV/TiO2/O3; however, the TOC removal did not vary among these systems. Adding ethanol reduced the decolorization rate of the UV/TiO2/O3 and O3/MnO2 systems and did not affect the decolorization rate of O3/Mn(II). Decolorization in UV/TiO2/O3, O3/Mn(II) and O3/MnO2 systems is suggested to proceed by mainly radical-, surface- and radical-type mechanisms, respectively. Additionally, direct ozonation cannot be ignored in O3/Mn(II) and O3/MnO2 systems.     

Degradation of C.I. Reactive Red 2 (RR2) using ozone-based systems: comparisons of decolorization efficiency and power consumption

This study investigated the decolorization efficiency of C.I. Reactive Red 2 (RR2) in O3, O3/H2O2, O3/Fe3+, O3/H2O2/Fe3+, UV/O3, UV/O3/Fe3+, UV/O3/H2O2 and UV/O3/H2O2/Fe3+ systems at various pHs. The effective energy consumption constants and the electrical energy per order of pollutant removal (EE/O) were also determined. The experimental results indicated that the energy efficiency was highest at [H2O2]0=1000mg/l and [Fe3+]0=25mg/l. Accordingly, the H2O2 and Fe3+ doses in the hybrid ozone- and UV/ozone-based systems were controlled at these values. This work suggests that the dominant reactant in O3, O3/Fe3+ and O3/H2O2 systems was O3 and that in the O3/H2O2/Fe3+ system was H2O2/Fe3+. The experimental results revealed that the combinations of Fe3+ or H2O2/Fe3+ with O3 at pH 4 and of H2O2 or H2O2/Fe3+ with UV/O3 at pH 4 or 7 yielded a higher decolorization rate than O3 and UV/O3, respectively. At pH 4, the EE/O results demonstrated that the UV/O3/H2O2/Fe3+ system reduced 85% of the energy consumption compared with the UV/O3 system. Moreover, the O3/H2O2/Fe3+ system reduced 62% of the energy consumption compared with the O3 system. At pH 7, the EE/O results revealed that the UV/O3/H2O2/Fe3+ system consumed half the energy of the UV/O3 system.     

Nitrogen and europium doped TiO2 anodized films with applications in photocatalysis

Micro-arc oxidation method is a useful process for mesoporous titanium dioxide films. In order to improve the photocatalytic activity of the TiO₂ film, N-Eu co-doped titania catalyst was synthesized by micro-arc oxidation in the H₂SO₄/Eu(NO₃)₃ mixture solution.The specific surface area and the roughness of the anodic titania film fabricated in the H₂SO₄/Eu(NO₃)₃ electrolyte, were increased compared to that of the anodic TiO₂ film prepared in H₂SO₄ solution. The absorbance response of N-Eu titania film shows a higher adsorption onset toward visible light region, and the incorporated N and Eu ions during anodization as a dopant in the anodic TiO₂ film significantly enhanced the photocatalytic activity for dye degradation. After dye decomposition test for 3 h, dye removal rates for the anodic TiO₂ film were 60.7% and 90.1% for the N-Eu doped titania film. The improvement of the photocatalytic activity was ascribed to the synergistic effects of the surface enlargement and the new electronic state of the TiO₂ band gap by N and Eu co-doping.     

Homogeneous catalytic ozonation of C.I. Reactive Red 2 by metallic ions in a bubble column reactor

This study elucidates the decolorization of C.I. Reactive Red 2 (RR2) by homogeneous catalytic ozonation. The effects of pH and catalyst dosage were evaluated in O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems. In O3/Mn(II), O3/Fe(II) and O3/Fe(III) systems, increasing the catalyst concentration increased the rate of RR2 decolorization; however, further increasing the catalyst concentration caused no further significant increase. When 0.6 mM catalyst was added, the decolorization rates of O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems at pH 2 were 3.295, 1.299, 1.278, 1.015, 0.843 and 0.822 min(-1), respectively. Under all of the experimental conditions, the decolorization efficiency of catalytic ozonation exceeded that of ozonation alone. The decolorization rate markedly exceeds the TOC removal rate in all tested systems. The effect of the radical scavenger on the catalytic ozonation processes suggests that the decolorization reaction in catalytic ozonation systems proceeds by mainly radical-type mechanisms, except in the O3/Mn(II) system.     

Synergistic effect in treatment of C.I. Acid Red 2 by electrocoagulation and electrooxidation

An aqueous C.I. Acid Red 2 solution was decolorized by electrolysis using iron as anode. The decolorization mechanism was investigated through experimental observations on the electrochemical behavior of C.I. Acid Red 2 on Pt rotating disk electrode, UV–visible spectra of the solution and IR spectra of the coagulated mixtures. It is found that the decolorization efficiency is high, over 98.0% after 40 min, and this high decolorization efficiency can be ascribed to the synergistic effect of electrocoagulation and electrooxidation. The electrocoagulation results from the electrogenerated iron hydroxide and the electrooxidation results from electrogenerated ferric ions. The results obtained from IR spectra shows that the decolorization of C.I. Acid Red 2 by electrooxidation is due to the partial or complete cleavage of C–N bonds in C.I. Acid Red 2.     

Effects of sonication on decolorization of C.I. Reactive Red 198 in UV/ZnO system

This study discusses the effects of ultrasound (US) irradiation on the decolorization of C.I. Reactive Red 198 (RR198) in UV/ZnO system. The influences of ZnO dosage, pH and the addition of NaCl or a radical scavenger were evaluated. The decolorization rate of RR198 increased with the ZnO dosage in 0.1-1g/l and with pH in the UV/ZnO system. US accelerated the decolorization of RR198 in the UV-based system. The enhancement in the presence of NaCl can be attributed to an increase in the partitioning of RR198 upon cavitation implosion in US/ZnO system. At pH 7, the decolorization rate constants of UV/US/ZnO, UV/ZnO, US/ZnO, UV/US and US were 0.0739, 0.0534, 0.0022, 0.0020 and 0.0013 min(-1), respectively. The decolorization rate was effectively inhibited by adding 1-butanol to UV/ZnO and UV/US/ZnO systems, suggesting that the main mechanism of RR198 destruction is chemical oxidation by hydroxyl radicals in the bulk liquid. The experimental results revealed that the UV/US/ZnO system cannot only completely decolorize RR198 but can effectively mineralize RR198.     

A template-free method to synthesize porous G-C3N4 with efficient visible light photodegradation of organic pollutants in water

Porous graphitic carbon nitride with a high surface area was successfully synthesized without using any template or other substances like metals, just by placing melamine powder into a muffle furnace which was heated to 550?°C in advance. To evaluate the structure, morphology, and optical properties, the high performance g-C₃N₄ (HPCN) was analyzed by XRD, SEM-EDX, TEM, N₂ physisorption, FT-IR analysis, UV–Vis DRS, PL, and Zeta potential. HPCN was able to completely degrade rhodamine B under visible light with the rate constant of 0.086?min^?1, which is 3.5 times higher than the traditional g-C₃N₄. The possible mechanism of RhB photodegradation was discussed in detail, which illustrated the reaction is performed in acidic media much better than neutral and basic solutions, and O₂^? and h⁺ are the key reactive species during the reaction. Moreover, the stability of the photocatalyst was investigated and turned out its photocatalytic activity has not considerably changed after 6 cycles, so it was a highly stable photocatalyst.     

Photocatalytic degradation of C.I. Direct Red 23 in aqueous solutions under UV irradiation using SrTiO3/CeO2 composite as the catalyst

The photocatalytic degradation of C.I. Direct Red 23 (4BS) in aqueous solutions under UV irradiation was investigated with SrTiO3/CeO2 composite as the catalyst. The SrTiO3/CeO2 powders had more photocatalytic activity for decolorization of 4BS than that of pure SrTiO3 powder under UV irradiation. The effects of catalytic dose, pH value, initial concentration of dye, irradiation intensity as well as scavenger KI were ascertained, and the optimum conditions for maximum degradation were determined. Under the irradiation of a 250 W mercury lamp, the best catalytic dose was 1.5 g/L and the best pH was 12.0. Light intensity exhibited a significant positive effect on the efficiency of decolorization, whereas the initial dye concentration showed a significant negative effect. Under the conditions of a catalytic dose of 1.5 g/L, pH of 12.0, initial dye concentration of 100mg/L, light intensity of 250 W, and air flow rate of 0.15 m3/h, complete decolorization, as determined by UV-visible analysis, was achieved in 60 min, corresponding to a reduction in chemical oxygen demand (COD) of 69% after a 240 min reaction. A tentative degradation pathway based on the sensitization mechanism of photocatalysis is proposed.     

Fabrication of fine-grained spherical tungsten powder by radio frequency (RF) inductively coupled plasma spheroidization combined with jet milling

Fine-grained spherical tungsten powder with particle size from 6 μm to 11 μm has been fabricated by a well-designed method with two simple steps. A pretreatment of tungsten powder was carried out in the first step. Complete dispersion, effective classification and favorable shape modification have been achieved by jet milling process. Accordingly, monodisperse tungsten powders with narrow particle size distribution were obtained. On the basis of the existing calculation and simulation results, plasma spheroidization parameters have been optimized. Thus, fine-grained spherical tungsten powder with narrow particle size distribution has been prepared by subsequent radio frequency (RF) inductively coupled plasma spheroidization. Furthermore, the presented method can be useful in fabricating spherical tungsten powder of different particle size with narrow particle size distribution as well as for process control in large-scale continuous production.     

磷酸处理HZSM-5负载TiO2光催化降解活性艳红X-3B

以磷酸改性的HZSM-5分子筛为载体,采用溶胶-凝胶法制备TiO2/HZSM-5光催化剂,通过XRD,SEM,BET,FT-IR和XPS进行表征。结果表明:TiO2均匀地分散在HZSM-5表面,没有发生TiO2颗粒的聚集。负载后的TiO2保持了锐钛矿晶体结构,TiO2的晶粒尺寸在负载后有所减小。TiO2/0.5HZSM-5的比表面积和对活性艳红X-3B的吸附量都随HZSM-5含量的增加而增加。负载后的TiO2光催化活性均高于纯TiO2,50%(质量分数)TiO2/0.5HZSM-5具有最高的活性,经紫外光照射2h可使活性艳红X-3B降解93.4%,而染料在纯TiO2上的降解率只有61.0%。     

纳米TiO2-Cu2O可见光下光催化降解活性艳红及其机理研究

采用钛酸丁酯水解和肼还原醋酸铜的方法制备出TiO2-Cu2O复合氧化物,研究了TiO2-Cu2O复合光催化剂在可见光照射下光催化降解活性艳红X-3B的性能,考察了催化剂组成、催化剂投加量、溶解氧、H2O2等对光催化反应的影响,探讨了Cu2O及TiO2-Cu2O光催化降解有机污染物的机理。结果表明,由于TiO2和Cu2O之间存在协同作用,使得复合氧化物的活性比单一的Cu2O高。Cu2O光催化的氧化物种为·OH和光生空穴。光生电子(e-)还原吸附在Cu2O表面上的氧,产生超氧阴离子,然后再进一步生成·OH,光生空穴(h+)无法直接将吸附在Cu2O表面的OH-氧化成·OH。     

Influence of ionic strength in the adsorption and during photocatalysis of reactive black 5 azo dye on TiO2 coated on non woven paper with SiO2 as a binder

Reactive black 5 (RB5), an azo dye, was degraded by using UV-irradiated TiO(2) coated on non woven paper with SiO(2) as a binder. The adsorption capacity of the photocatalyst was studied at natural pH, superior to pH(pzc) of the binder, for various ionic strengths. Different salts such as NaCl, KCl, CaCl(2), LiCl, Ca(NO(3))(2) were used to increase the ionic strength. The presence of salt increased the adsorption capacity. The electrostatic interactions between dye and oxide surface charges (TiO(2)/SiO(2)) is very important in the adsorption phenomena. The effect of the ionic strength of the solution on photocatalyst degradation was studied. The rate of degradation was increased by the presence of salts in the range of the experimental conditions. The increase of the initial decolorization rate was observed in the following order: Ca(2+)>K(+)>Na(+)>Li(+). Experiments with different anions (Cl(-), NO(3)(-)) had shown that nitrate was an indifferent electrolyte for the adsorption and photodegradation of the dye on SiO(2)/TiO(2).     

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N₂ adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298 K was fixed at 1 h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323 K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment.     

An Evaluation of Metronidazole Degradation in a Plasma-Assisted Rotating Disk Reactor Coupled with TiO2 in Aqueous Solution

Pollution involving pharmaceutical components in bodies of water is an increasingly serious environmental issue. Plasma discharge for the degradation of antibiotics is an emerging technology that may be relevant toward addressing this issue. In this work, a plasma-assisted rotating disk reactor (plasma-RDR) and a photocatalyst—namely, titanium dioxide (TiO₂)—were coupled for the treatment of metronidazole (MNZ). Discharge uniformity was improved by the use of a rotating electrode in the plasma-RDR, which contributed to the utilization of ultraviolet (UV) light radiation in the presence of TiO₂. The experimental results showed that the degradation efficiency of MNZ and the concentration of generated hydroxyl radicals respectively increased by 41% and 2.954 mg∙L⁻¹ as the rotational speed increased from 0 to 500 r∙min⁻¹. The synergistic effect of plasma-RDR plus TiO₂ on the generation of hydroxyl radicals was evaluated. Major intermediate products were identified using three-dimensional (3D) excitation emission fluorescence matrices (EEFMs) and liquid chromatography–mass spectrometry (LC-MS), and a possible degradation pathway is proposed herein. This plasma-catalytic process has bright prospects in the field of antibiotics degradation.     

Pre-ozonation coupled with UV/H2O2 process for the decolorization and mineralization of cotton dyeing effluent and synthesized C.I. Direct Black 22 wastewater

The decolorization and mineralization of cotton dyeing effluent containing C.I. Acid Black 22 as well as synthesized C.I. Acid Black 22 wastewater by means of advanced oxidation processes (AOPs), such as UV/H2O2, O3 and pre-ozonation coupled with UV/H2O2 processes, were evaluated in this study. It was observed that the UV/H2O2 process took longer retention time than ozonation for color removal of dye bath effluent. Reversely, the total organic carbon (TOC) removal showed different phenomena that ozonation and UV/H2O2 process obtained 33 and 90% of removal efficiency for 160 min of retention time, respectively. Additionally, laboratory synthesized dye wastewater was substantially more efficient in the decolorization process than dye bath effluent. Therefore, in this work, pre-ozonation coupled with UV/H2O2 process was employed to enhance the reduction of both color and TOC in dye bath effluent at the same time. At the same time, the retention time demand was reduced to less than 115 min for 90% removal of TOC and color by this combined process.     

Degradation of dyehouse effluent containing C.I. Direct Blue 199 by processes of ozonation, UV/H2O2 and in sequence of ozonation with UV/H2O2

The decolorization and mineralization of cotton dyeing effluent containing C.I. Direct Blue 199 (DB 199) by advanced oxidation processes (AOPs) such as ozonation, UV/H(2)O(2), and in sequence of ozonation with UV/H(2)O(2) processes were evaluated in this study. By ozonation alone, the color removal was almost 100% for DB 199 and greater than 80% for dye bath effluent rapidly within 5 and 15 min, respectively. Meanwhile, the reduction of total organic carbon (TOC) was about 60% for DB 199 and almost no change for dye bath effluent, respectively due to incomplete mineralization. On the other hand, by UV/H(2)O(2) alone, the color removing not only took longer time but obtained lower removal efficiencies for DB 199 and dye bath effluent about 80% and 95% in 30 and 120 min, respectively. Nevertheless, it was more effective than ozonation for TOC removal while about 75% and 80% in 30 and 120 min, respectively. As a result, this study conducted the combination with the above two processes in order to shorten time demand as well as the higher removal efficiencies of both color and TOC simultaneously. Thus, the sequence process was designed to begin with ozonation to rapidly remove color proficiently, following by UV/H(2)O(2) in order to promptly remove remaining TOC efficiently. The successful process design by sequence of ozonation with UV/H(2)O(2) has proved the significant improvement for the removal of both color and TOC in dye bath effluent shortly. Besides, the lab prepared dye solution was substantially much easier to be decolorized than field dye bath effluent so that the lab results were utilized to design the further applications of pilot or full scale.     

Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions

Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na₂SO₄ as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO₂–Sb–Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV–visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.     

Influence of organic and inorganic compounds on oxidoreductive decolorization of sulfonated azo dye C.I. Reactive Orange 16

An isolated bacterial strain is placed in the branch of the Bacillus genus on the basis of 16S rRNA sequence and biochemical characteristics. It decolorized an individual and mixture of dyes, including reactive, disperse and direct. Bacillus sp. ADR showed 88% decolorization of sulfonated azo dye C.I. Reactive Orange 16 (100 mg L⁻¹) with 2.62 mg of dye decolorized g⁻¹ dry cells h⁻¹ as specific decolorization rate along with 50% reduction in COD under static condition. The optimum pH and temperature for the decolorization was 7–8 and 30–40 °C, respectively. It was found to tolerate the sulfonated azo dye concentration up to 1.0 g L⁻¹. Significant induction in the activity of an extracellular phenol oxidase and NADH–DCIP reductase enzymes during decolorization of C.I. Reactive Orange 16 suggest their involvement in the decolorization. The metal salt (CaCl₂), stabilizers (3,4-dimethoxy benzyl alcohol and o-tolidine) and electron donors (sodium acetate, sodium formate, sodium succinate, sodium citrate and sodium pyruvate) enhanced the C.I. Reactive Orange 16 decolorization rate of Bacillus sp. ADR. The 6-nitroso naphthol and dihydroperoxy benzene were final products obtained after decolorization of C.I. Reactive Orange 16 as characterized using FTIR and GC–MS.     

Rapid decolourization and mineralization of the azo dye C.I. Acid Red 14 by heterogeneous Fenton reaction

The decolourization and mineralization of a solution of an azo dye using a catalyst based on Fe(II) supported on Y Zeolite (Fe(II)-Y Zeolite) and adding hydrogen peroxide (heterogeneous Fenton process) have been studied. The catalyst was prepared by ion exchange, starting from a commercial ultra-stable Y Zeolite. All experiments were performed on a laboratory scale set-up. The effects of different parameters such as initial concentration of the dye, initial pH of the solution of the dye, H(2)O(2) concentration, temperature and ratio of amount of catalyst by amount of solution on the decolourization efficiency of the process were investigated. A percentage of colour removal of 99.3±0.2% and a mineralization degree of 84±5% of the solution of the dye were achieved in only 6 min of contact time between the catalyst and the solution, under the following conditions: initial concentration of the dye of 50 ppm, pH 5.96, 8.7 mM of H(2)O(2), T of 80°C and catalyst concentration of 15 g/L. Moreover, the catalyst Fe(II)-Y Zeolite can be easily filtered from the solution, does not leach any iron into the solution (avoiding any secondary contamination due to the metal) and its effectivity can be reproduced after consecutive experiments.