Treatment of dilute methylene blue-containing wastewater by coupling sawdust adsorption and electrochemical regeneration

In the present work, the coupling of adsorption and electrochemical oxidation on a boron-doped diamond (BDD) electrode to treat solutions containing dyes is studied. This coupling may be convenient for the treatment of diluted pollutant that is limited by the low rate of electrooxidation due to mass-transfer limitation. A pre-concentration step by adsorption could minimize the design of the electrochemical reactor. The adsorbent chosen was mixed with softwood sawdust, and methylene blue was chosen as the model dye molecule. Isotherms of adsorption and kinetics were investigated as well as the effects of current density and regeneration time. The BDD electrochemical oxidation of methylene blue adsorbed onto sawdust led simultaneously to its degradation and sawdust regeneration for the next adsorption. It was observed that multiple adsorption and electrochemical regeneration cycles led to an enhancement of adsorption capacity of the sawdust. This study demonstrated that adsorption–electrochemical degradation coupling offers a promising approach for the efficient elimination of organic dyes from wastewater.     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

Photochemically-assisted electrochemical degradation of landfill leachate

In this work, the treatment of landfill leachates by a photoelectrochemical procedure is reported. When applied to untreated leachates the photochemical system was significantly hindered on account of the characteristic dark coloration of the samples. At this condition the degradation process was essentially electrochemical permitting typical color and COD removal of about 50% and 20%, respectively. When a previous chemical precipitation process was applied aiming the elimination of colored species (mainly humic substances) the decolorization and COD removal was extended to 90% and 60%, respectively. Considering the extremely complex character of the leachates and its usual resistance to conventional degradation processes the result reported here attest the high potentiality of photoelectrochemical processes to remediation of recalcitrant residues.     

碳纳米管电极原位产生过氧化氢及其对亚甲基蓝脱色效果简

将碳纳米管固定化制成多孔疏水性导电薄膜构建电化学阴极还原体系，实现过氧化氢在阴极的原位产生。电极特性研究表明，电极在较宽的电压范围内均具有较好的活性。考察了阴极电位、电极成分、氧气流量和电解质浓度对过氧化氢原位产生的影响，在优化条件下经过120 min后过氧化氢达到66.17 mg/L，并探讨过氧化氢原位产生的机理。在此基础上考察原位过氧化氢氧化工艺下对亚甲基蓝的脱色效果，并分析其脱色机理。     

碳纳米管电极原位产生过氧化氢及其对亚甲基蓝脱色效果

将碳纳米管固定化制成多孔疏水性导电薄膜构建电化学阴极还原体系，实现过氧化氢在阴极的原位产生。电极特性研究表明，电极在较宽的电压范围内均具有较好的活性。考察了阴极电位、电极成分、氧气流量和电解质浓度对过氧化氢原位产生的影响，在优化条件下经过120min后过氧化氢达到66．17mg／L，并探讨过氧化氢原位产生的机理。在此基础上考察原位过氧化氢氧化工艺下对亚甲基蓝的脱色效果，并分析其脱色机理。     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Ru-TiO2光电极对亚甲基蓝的光电催化降解

采用阳极氧化法制备Ru—TiO2光电极，以该电极为工作电极，石墨作对电极，饱和甘汞电极为参比电极，对亚甲基蓝溶液的光电催化降解进行了研究。结果表明：煅烧温度600oC，掺杂1％Ru的Ru-TiO2光电极催化活性最好；以紫外灯（125W）为光源，当外加偏压0．2V，pH为5时，Ru-TiO2光电催化亚甲基蓝120min可使其完全脱色；亚甲基蓝的光电催化降解遵从Langmuir—Hinshelwood动力学模型，测得其反应速率常数k：0．781mmol／（L·min），吸附常数K=0．225L／mmol。     

Ru-TiO_2光电极对亚甲基蓝的光电催化降解

采用阳极氧化法制备Ru-TiO2光电极,以该电极为工作电极,石墨作对电极,饱和甘汞电极为参比电极,对亚甲基蓝溶液的光电催化降解进行了研究。结果表明:煅烧温度600℃,掺杂1%Ru的Ru-TiO2光电极催化活性最好;以紫外灯(125 W)为光源,当外加偏压0.2 V,pH为5时,Ru-TiO2光电催化亚甲基蓝120 min可使其完全脱色;亚甲基蓝的光电催化降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k=0.781 mmol/(L.min),吸附常数K=0.225 L/mmol。     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

新型二氧化铅电极处理染料废水

利用高压塑片法制备掺杂镧和活性炭以及聚四氟乙烯(PTFE)的新型二氧化铅电极,采用X衍射(XRD),循环伏安曲线(CV),扫描电镜(SEM)等手段对电极性能进行表征,研究了其电催化处理有机染料废水(亚甲基蓝)的降解效果,并对反应机理进行了相关研究。研究表明,该电极具有良好的抗腐蚀能力,对亚甲基蓝具有较好的降解效果。通过与普通二氧化铅电极比较,该电极在染料脱色和去除COD方面都有较明显优势,显示出较好的工业应用前景。     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of phenol over monoclinic BiVO4 under visible light irradiation

BiVO4 powder with monoclinic structure was prepared and used as a visible-light catalyst simultaneously for the photooxidation of phenol and the photoreduction of Cr(VI). The photocatalytic efficiency was found to be rather low for either single phenol solution or single Cr(VI) solution. However, the photocatalytic reduction of Cr(VI) and photocatalytic oxidation of phenol proceed more rapidly for the coexistence system of phenol and Cr(VI) than for the single process, showing synergetic effect between the oxidation and reduction reactions. For the simultaneous photocatalytic reduction-oxidation process, the first-order kinetic constant of phenol degradation was 0.0314 min-1, being about six times higher than that for the photocatalytic process of single phenol. This result reveals the feasibility of using Cr(VI) as the electron scavenger of mBiVO4-mediated photocatalytic process of phenol degradation, and gives us an enlightenment to employ other semiconductor with a better visible light response but with a more positive band edge to efficiently degrade organic pollutants. This is the first report for simultaneous photocatalytic reduction of Cr(VI) and removal of phenol under visible light irradiation using photocatalyst mBiVO4.     

Solar photocatalytic decolorization of methylene blue in water

In this study, a photocatalytic decolorization system equipped with immobilized TiO2 and illuminated by solar light was used to remove the color of wastewater. To examine the decoloring efficiency of this system, photocatalytic decolorization of an organic dye such as methylene blue was studied as an example. The effects of light source, pH, as well as the initial concentration of dye were also investigated. It was observed that the solution of methylene blue could be almost completely decolorized by the solar light/TiO2 film process while there was about 50% color remaining with solar irradiation only. In addition, it was found that the decoloring efficiency of solution was higher with solar light irradiation than with artificial UV light irradiation, even though the artificial UV light source supplied higher UV intensity at 254 nm. The color removal rate of methylene blue with solar light irradiation was almost twice that of artificial UV light irradiation. This phenomena was mainly attributed to that some visible light range of solar light was useful for exciting the methylene blue molecules adsorbed on TiO2 film, leading to a photosensitization process undergoing and decoloring efficiency promoted. This solar-assisted photocatalytic device showed potential application for decoloring organic dyes in wastewater.     

Gadolinium nanoparticle-decorated multiwalled carbon nanotube/titania nanocomposites for degradation of methylene blue in water under simulated solar light

Gadolinium oxide nanoparticles of diameters <5 nm were uniformly decorated on the surfaces of multiwalled carbon nanotubes which were subsequently used as templates to fabricate gadolinium oxide nanoparticle-decorated multiwalled carbon nanotube/titania nanocomposites. The prepared nanocomposites were evaluated for the photocatalytic degradation of methylene blue under simulated solar light irradiation. Higher photocatalytic activity was observed for the gadolinium oxide-decorated multiwalled carbon nanotube-based nanocomposites compared to the neat multiwalled carbon nanotube/titania nanocomposite and commercial titania. This improvement in photocatalytic activity was ascribed to the gadolinium oxide nanoparticles supported at the interface of the carbon nanotubes and titania resulting in efficient electron transfer between the two components of the composite. Total organic carbon (TOC) analysis revealed a higher degree of complete mineralisation of methylene blue (80.0 % TOC removal) which minimise the possible formation of toxic by-products. The photocatalyst could be re-used for five times, reaching a maximum degradation efficiency of 85.9 % after the five cycles. The proposed photocatalytic degradation mechanism is outlined herein.     

LiFePO_4非均相Fenton法处理亚甲基蓝染料的研究

采用水热法制备出LiFePO4催化剂,通过电子显微镜（SEM）、X射线衍射（XRD）和傅立叶红外光谱（FTIR）对其进行表征,并将其作为非均相Fenton催化剂处理亚甲基蓝（MB）染料溶液。实验结果表明,在催化剂用量为4 g/L,H2O2浓度为0.04 mol/L,pH值为3,温度为50℃,反应时间为60 min的条件下,浓度为500 mg/L的亚甲基蓝脱色率达99%。根据实验结果,讨论了LiFePO4作为非均相Fenton催化剂对亚甲基蓝的降解机理。     

LiFePO4非均相Fenton法处理亚甲基蓝染料的研究

采用水热法制备出LiFePO4催化剂,通过电子显微镜(SEM)、X射线衍射(XRD)和傅立叶红外光谱(FTIR)对其进行表征,并将其作为非均相Fenton催化剂处理亚甲基蓝(MB)染料溶液。实验结果表明,在催化剂用量为4 g/L,H2O2浓度为0.04 mol/L,pH值为3,温度为50℃,反应时间为60 min的条件下,浓度为500 mg/L的亚甲基蓝脱色率达99%。根据实验结果,讨论了LiFePO4作为非均相Fenton催化剂对亚甲基蓝的降解机理。     

Electrochemical decolourisation of structurally different dyes

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.     

Degradation of carbofuran in water by solar photocatalysis in presence of photosensitizers

The effect of the presence of photosensitizers, methylene blue (MB) and rose Bengal (RB), on the degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) in water in a solar photocatalytic system was investigated. It was found that as compared to MB, RB generally showed a stronger effect on the decomposition of carbofuran under comparable conditions. Among the conditions studied, adding 2 x 10(-6) M of RB, that corresponding to 2% of the initial concentration of carbofuran solution in the system, rendered the most effective degradation of carbofuran. As a result, a carbofuran removal percentage of 69.9%, a mineralization efficiency of 28.0%, and a microtoxicity reduction of 65.0% could be achieved. The degradation and mineralization of carbofuran was found to follow the pseudo-first order reaction kinetics. The decomposition mechanism of carbofuran was further investigated through identification of the intermediates to elaborate the influence of dye photosensitizer on the solar photocatalysis of carbofuran in water. On the basis of the intermediates identified, including carbofuran phenol, 3-hydroxy carbofuran phenol, and substituted alcohols (3-phenoxy 1-propanol, 2-ethyl 1-hexanol, 2-butoxyl ethanol), it appears that hydrolysis and hydroxylation were the two key mechanisms for decomposing carbofuran during the process of solar photocatalysis with the aid of dye photosensitizer.     

花生壳活性炭对亚甲基蓝的吸附特性

以花生壳为原料,氯化锌为活化剂制备花生壳活性炭,采用高分辨电子扫描电镜(SEM)和氮吸脱附曲线对花生壳活性炭进行了表征.从热力学和动力学的角度,研究了花生壳活性炭对亚甲基蓝溶液的吸附行为.热力学研究表明,花生壳活性炭对亚甲基蓝的吸附符合Langmuir等温吸附方程,该吸附是自发吸热过程,吸附自由能为-52.4017～-95.1765 kJ/mol,吸附熵变为214 J/(mol·K),吸附焓变为57.49796 kJ/mol.动力学研究表明,花生壳活性炭对亚甲基蓝的吸附符合二级反应动力学方程反应特征.     

Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

Treatment of landfill leachate by electrochemical oxidation and anaerobic process.

The removal performance of typical refractory organic compounds in landfill leachate was investigated during the electrochemical (EC) oxidation and anaerobic process combined treatment system in this paper. The results indicated that the treatment of landfill leachate by the combined system was highly effective. The toxicity of leachate was notably decreased after the electrochemical oxidation process and the biodegradability was improved. The concentration of the organic acid with low molecular weight in the leachate increased from 28% to 90% based on the biodegradability assays after the EC oxidation process. The anaerobic digestion could further remove the residual organic compounds. At a hydraulic retention time (HRT) of 16 hours and an organic loading rate (OLR) of 8 kg COD/m3 d, the concentration of COD, SS, ALK, VA, N-TKN, N-NH4+ and P-PO4(3)- [corrected] in UASB effluent were 532, 12, 6744, 400, 540, 455 and 11.6 mg/L, respectively, with approximately 90% removal efficiency of COD. The organic compounds in the landfill leachate revealed different degradation characteristics in the combined system. p-chloroaniline, bisphenol A, 6-methyl-2-phenyl-quinoline, dimethylnaphthaline and N'-(2-methyl-4-chlorophenyl)-N-cyclohexyformamidine, classified into the first group in this paper, were completely removed by the EC oxidation and did not reappear in the effluent of the UASB reactor. Phenylacetic acid, 3-methyl-indole and N-cyclohexyl-acetamide, called the second group, were completely removed, but reappeared in the UASB reactor. 4-methyl-phenol, 3,4-dihydroisoquinoline, 2(3H)-benzothiazolone, exo-2-hydroxycineole and benzothiazole, the third group, were degraded little in the EC oxidation process, but extensively removed by the anaerobic process. Benzoic acid, benzenepropanoic acid and 2-cyano-3,5-dimethyl-1-hydroxypyrrole, the fourth group, concentration obviously increased in the EC process, but was completely removed in the UASB reactor. The content of volatile fatty acids (VFAs) markedly increased from 0.68% in the leachate to 16.18% in the effluent from the electrochemical oxidation process (EC(effl)). In addition, the degradation rate of organic compounds from the landfill leachate was different in the EC oxidation and anaerobic process.