Design of a neutral electro-Fenton system with Fe@Fe(2)O(3)/ACF composite cathode for wastewater treatment

The narrow pH range limits the wide application of Fenton reaction in the wastewater treatment. It is of great importance to widen working pH range of Fenton reaction from strong acidic condition to neutral, even basic ones. In this study, for the first time nanostructured Fe@Fe(2)O(3) was loaded on active carbon fiber (ACF) as an oxygen diffusion cathode to be used in a heterogeneous electro-Fenton (E-Fenton) oxidation system. This novel Fe@Fe(2)O(3)/ACF composite cathode was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), and element mapping. On the degradation of dye pollutant rhodamine B in water, this heterogeneous E-Fenton system with the Fe@Fe(2)O(3)/ACF cathode showed much higher activity than other E-Fenton systems with commercial zero valent iron powders (Fe(0)) and ferrous ions (Fe(2+)) under neutral pH. On the basis of experimental results, we proposed a possible pathway of rhodamine B degradation in this heterogeneous Fe@Fe(2)O(3)/ACF E-Fenton process. This heterogeneous E-Fenton system is very promising to remove organic pollutants in water at neutral pH.     

Degradation of bisphenol A in aqueous solution by H2O2-assisted photoelectrocatalytic oxidation

A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.     

Preparation of Pd/GO/Ti electrode and its electrochemical degradation for 2,4-dichlorophenol

It has been well-known that 2,4-dichlorophenol (2,4-DCP) is a refractory organic substance which is difficult to treat via traditional treatment process. In this research, a novel palladium (Pd)/graphene oxide (GO)/Ti electrode was modified with electrochemical-deposition method for the degradation of 2,4-DCP via electrochemical degradation process. The structure, morphology and characteristics of the electrode were observed and analyzed with various detecting methods such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The 2,4-DCP degradation performance was examined with the Pd/GO/Ti electrode under various electrical current intensity of 5, 10 and 20 mA. The highest removal rate of 2,4-DCP was 92.2% obtained under 5 mA. The removal rate of 10 mA was 91.9%, while that of 20 mA was 90.9%. The removal rate has no significant response with the changes of current. Hence, the degradation of 2,4-DCP by the Pd/GO/Ti electrode followed pseudo-first-order reaction under different currents.     

Comparison treatment of various chlorophenols by electro-Fenton method: relationship between chlorine content and degradation

This study describes a comparative degradation of various chlorophenols by electro-Fenton method. Chloride released and reaction intermediate products were determined by ionic chromatography (IC) and gas chromatography/mass spectrometry (GC/MS). Using pentachlorophenol (PCP) as the model compound, we investigated the effects of cell voltage, electrolyte concentration and pH to optimize the degradation conditions. It was noted that the addition of small quantities of Fe3+ or Fe2+ significantly accelerated the degradation rate. Under the optimal conditions, electro-Fenton method was used to treat various chlorophenols including PCP, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and their mixture aqueous solutions. Their pseudo first-order degradation rate constants at the first stages were calculated and compared, which gave the following sequence: 2,4-DCP>2,4,6-TCP>PCP>4-CP. The relationship between the chlorine content and degradation rate was discussed and compared with other advanced oxidation processes. Finally, we proposed the degradation pathways of different chlorophenols.     

Effects of iron type in Fenton reaction on mineralization and biodegradability enhancement of hazardous organic compounds

The mineralization and biodegradability increase and their combination of two traditional and two relatively new organic contaminants by Fenton reagents with three different types of iron, Fe(2+), Fe(3+), and Fe(0) were investigated. The traditional contaminants examined were trichloroethene (TCE) and 2,4-dichlorophenol (2,4-DCP) while 1,4-dioxane (1,4-D) and 1,2,3-trichloropropane (TCP) were studied for the relatively new contaminants. The mineralization and biodegradability were represented by dissolved organic carbon (DOC) reduction and the ratio of biodegradable dissolved organic carbon and DOC, respectively. For all four contaminants, Fenton reagent using Fe(2+) was more effective in the DOC reduction than Fenton reagents using Fe(3+) and Fe(0) in most cases. The types of Fe that provided maximum biodegradability increase were not the same for all four compounds, Fe(3+) for TCE, Fe(0) for 2,4-DCP, Fe(2+) for 1,4-D, and Fe(3+) for TCP. When the combination of DOC elimination and biodegradability increase (least refractory fraction) was considered, Fe(2+) was the best choice except for 2,4-DCP which was susceptible to Fe(0) catalyzed Fenton reagent the most. The least refractory fractions remaining after 120 min of reaction were 20-25% for TCE, 2,4-DCP, and TCP and 30-40% for 1,4-D. The iron type in Fenton reaction also affected the type of mineralization kinetics of TCE, 2,4-DCP, and TCP as well as the types of degradation by-products of these contaminants. Some of the by-products found, such as isopropanol and propionic aldehyde, which were produced from Fe(0) catalyzed Fenton degradation of TCP, have not been previously reported.     

双阳极光电催化氧化降解2,4-二氯苯酚的研究

为提高高级氧化技术对内分泌干扰物的降解和矿化性能,首次研究了(TiO2/Ti-Fe)-石墨毡双阳极光电协同催化氧化体系,并考察了其对2,4-二氯苯酚的光催化氧化降解性能.研究了电流在TiO2/Ti-Fe两阳极上的分配,外加电压,pH等主要因素对2,4-二氯酚降解效率的影响及反应过程中H2O2的生成及积累情况.实验结果表明,本体系不仅具有较高的H2O2生成效率和较强的光催化氧化降解性能,而且该体系可以在较宽的pH范围内工作.在较低的电流密度下反应60 min,2,4-二氯酚的降解率可达95%以上,而矿化率高达80%.     

Anodic destruction of 4-chlorophenol solution

The electrochemical oxidation of 4-chlorophenol solutions was studied using a dimensional stable anode (DSA), made of pure titanium sheet mesh coated with Ti/TiO(2) and RuO(2) film. An electrochemical cell with one working electrode and two counter-electrodes was designed. A gas collecting system to collect the electrolysis gaseous products was also designed. The influence of current density (6.51-21.58 mA/cm(2)), pH (2.0-12.6) and initial 4-chlorophenol concentration (25-100 mg/l) on the destruction was investigated. Complete elimination was successfully achieved within 2 h for most investigated conditions. Highest rates of elimination were achieved at a pH of 12.6.A new approach to calculate the current efficiency (CE) of the cell was proposed. The volumes of the gases produced at the anode and at the cathode were the basis for the new CE calculations. It was observed that the worst CE was approximately 20% and the best CE was approximately 89%. The most efficient pH was at 12.6 and the most efficient current density was at 11.39 mA/cm(2).     

Novel synthesis of Cu-HAP/SiO2@carbon nanocomposites as heterogeneous catalysts for Fenton-like oxidation of 2,4-DCP

Hydroxyapatite (HAP) has stable ion exchange capacity and is a potential environmental catalyst carrier. In this paper, a novel metal–carbon nanocomposite (Cu-HAP/SiO₂@carbon) was synthesized as a catalyst to remove 2,4-DCP. The SEM, XRD, FT-IR, XPS and BET were used to characterize the synthesized catalyst materials, the results showed that Cu-HAP/SiO₂@carbon has a rich pore structure and a high specific surface area, and the copper element is well dispersed on the surface of the carrier. The results of 2,4-DCP removal effect showed that almost 100 % of 2,4-DCP was removed under the optimal reaction conditions. In addition, the Cu-HAP/SiO₂@carbon broaden the applicable pH range and has excellent performance in terms of reusability (93.73 % of removal rate after 5 cycles). Finally, based on the intermediate products identify by HPLC, the degradation mechanism and possible degradation pathway of 2,4-DCP was investigated, EPR was employed to confirm the effects of ·OH.     

Catalytic dechlorination of 2,4-dichlorophenol by Ni/Fe nanoparticles in the presence of humic acid: intermediate products and some experimental parameters

The catalytic dechlorination of 2,4-dichlorophenol (2,4-DCP) by Ni/Fe bimetallic nanoparticles in the presence of humic acid (HA) was investigated in order to understand their applicability for in situ remediation of groundwater. 2,4-DCP was catalytically dechlorinated to form the final products – phenol (P) via two intermediates, o-chlorophenol (o-CP) and p-chlorophenol (p-CP). It was demonstrated that the carbon mass balances during the dechlorination were between 84% and 92%, and other carbons were adsorbed on the surface of Ni/Fe bimetallic nanoparticles. The experimental results suggest that HA competed for reaction sites on the Ni/Fe bimetallic nanoparticles with 2,4-DCP, and thus reduced the efficiency and rate of the dechlorination of 2,4-DCP. The catalytic degradation slowed down as the increase of HA in solution, and when HA's concentrations were 0, 10, 20 and 30?mg?L^?1, the maximum concentrations of o-CP were 0.025, 0.041, 0.039 and 0.034?mM in 10, 30, 30 and 30?min, respectively. High Ni content, low initial pH value, high Ni/Fe nanoparticles’ dosage and high temperature favoured the catalytic dechlorination of 2,4-DCP. The experimental results show that no other intermediates were generated besides Cl^?, o-CP, p-CP and P during the catalytic dechlorination of 2,4-DCP.     

Al-TiO2-C-Ti-Fe体系反应过程研究

采用ＤＳＣ和ＸＲＤ对不同Ｆｅ含量Ａｌ－ＴｉＯ２－Ｃ－Ｔｉ－Ｆｅ体系的燃烧反应过程进行了研究。结果表明,Ａｌ－ＴｉＯ２－Ｃ－Ｔｉ－Ｆｅ体系的反应是分步进行的。在高温区以金属间化合物的分解及Ｔｉ、Ｃ反应为主;在低温区则随着Ｆｅ含量的不同存在不同的反应：Ａｌ－ＴｉＯ２－Ｃ－Ｔｉ以Ａｌ、Ｔｉ的反应为主,Ａｌ－ＴｉＯ２－Ｃ－Ｔｉ－２０ｗｔ％Ｆｅ以Ａｌ、Ｔｉ及Ａｌ、Ｆｅ反应为主,同时还存在Ａｌ、ＴｉＯ２及Ｆｅ、Ｔｉ反应,而Ａｌ－ＴｉＯ２－Ｃ－Ｔｉ－５０ｗｔ％Ｆｅ则以Ｆｅ、Ａｌ和Ｆｅ、Ｔｉ反应为主。     

Degradation of 2,4-dichlorophenol by using glow discharge electrolysis

Degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous by glow discharge electrolysis (GDE) has been investigated. Ultraviolet (UV) absorption spectra, atomic force microscopy (AFM), high performance liquid chromatography (HPLC) and gas chromatogram-mass spectrum (GC/MS) are used to monitor the degradation process and to identify the major oxidation intermediate products. It has been found that 2,4-DCP undergoes a series of intermediate step, which leads to form a number of intermediate products, mainly isomeric chlorophenols and aliphatic acids. These products are further oxidized, eventually, mineralized into CO(2) and Cl(-). A degradation pathway for 2,4-DCP is proposed on the basis of detection of intermediate compounds.     

光电催化降解有机污染物与回收银分析

报道了在光电反应器中,TiO2阳极光催化降解典型有机污染物水杨酸的同时,光生电子在外加电场的作用下驱动到对电极上还原回收银.研究结果表明,随着外加阳极偏压增大,光电流不断增大并在一定的偏压下达到饱和,有机物氧化速率提高.银离子的还原速率受阴极槽的气氛、溶液pH和外加阳极偏压(电流)等因素的影响,但在三电极光电反应器中,阳极反应的快慢直接决定阴极反应类型和反应速率.本实验条件下,银离子的沉积电流效率高达96.0%,采用该方法不但可充分地利用光生载流子,而且可避免催化剂的失活问题,从而拓宽了光催化技术的应用范围.     

Treatment of nitrophenols by cathode reduction and electro-Fenton methods

This study deals with the degradation of various nitrophenols by cathode reduction and electro-Fenton methods. Phenols (Poh), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), and 2,4-dinitrophenol (2,4-DNP) are treated and different degradation sequences are obtained. The relationship between the structure and activities of nitrophenols is discussed. Using 4-NP as a model nitrophenol, the electrochemical behaviors on graphite cathode and Pt anode are analyzed by cyclic voltammetry. The contribution of different reactions to the degradation of 4-NP is investigated in divided cells. The degradation of 4-NP is much faster in the cathode cell than in the anodic cell. In the cathode cell, the degradation of 4-NP is significantly enhanced by the introduction of aeration and Fe(2+). Ultraviolet-visible (UV-vis) spectra reveal different reaction pathways for the degradation in the anodic cell and cathode cell. Treatment of high concentration of 4-NP in the undivided cell shows that more than 98% removal of 4-NP and about 13% removal of total organic carbon (TOC) are obtained for both processes, while the subsequent biodegradability test shows that electro-Fenton can eliminate the toxicity and improve the biodegradability of 4-NP. Negligible quantity of nitrate and nitrite ions detected in both processes indicates that there is no direct release of -NO(2) and -NO groups from 4-NP and its degradation intermediates. Intermediates such as hydroquinone and bezoquinone are detected by gas chromatography/mass spectrum (GC/MS). The degradation pathway of 4-NP in electro-Fenton process is proposed as the cathode reduction followed by hydroxyl oxidation.     

Photocatalytic degradation of 2,4-dinitrophenol

Contamination of the food supply from agricultural waste is an increasing concern worldwide. Numerous hazardous chemicals enter the environment from various industrial sources daily. Many of these pollutants, including 2,4-dinitrophenol (2,4-DNP), are water soluble, toxic, and not easily biodegradable. The solar photocatalytic degradation of 2,4-DNP was investigated in a solution of titanium dioxide (TiO(2)) that was prepared to be an optically clear aqueous solution of nanosized particles of TiO(2). In order to achieve optimal efficiency of the photodegradation, the effects of light intensity and pH were conducted. All experiments were carried out in a batch mode. At a pH of 8, maximum removal of 70% of 2,4-DNP was achieved within 7h of irradiation time. The nearly homogeneous solution of 5.8nm TiO(2) particles, size determined by XDS, were very effective in the photocatalytic degradation of 2,4-DNP.     

The cooperative electrochemical oxidation of chlorophenols in anode-cathode compartments

By using a self-made carbon/polytetrafluoroethylene (C/PTFE) O2-fed as the cathode and Ti/IrO2/RuO2 as the anode, the degradation of three organic compounds (phenol, 4-chlorophenol, and 2,4-dichlorophenol) was investigated in the diaphragm (with terylene as diaphragm material) electrolysis device by electrochemical oxidation process. The result indicated that the concentration of hydrogen peroxide (H2O2) was 8.3 mg/L, and hydroxyl radical (HO) was determined in the cathodic compartment by electron spin resonance spectrum (ESR). The removal efficiency for organic compounds reached about 90% after 120 min, conforming to the sequence of phenol, 4-chlorophenol, and 2,4-dichlorophenol. And the dechlorination degree of 4-chlorophenol exceeded 90% after 80 min. For H2O2, HO existed in the catholyte and reduction dechlorination at the cathode, the mineralization of organics in the cathodic compartment was better than that in the anodic compartment. The degradation of organics was supposed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H2O2, HO produced by oxygen reduction at the cathode. High-performance liquid chromatography (HPLC) allowed identifying phenol as the dechlorination product of 4-chlorophenol in the cathodic compartment, and hydroquinone, 4-chlorocatechol, benzoquinone, maleic, fumaric, oxalic, and formic acids as the main oxidation intermediates in the cathodic and anodic compartments. A reaction scheme involving all these intermediates was proposed.     

Degradation of 4-nitrophenol in aqueous medium by electro-Fenton method

The degradation of 4-nitrophenol by electro-Fenton (E-Fenton) method was carried out in batch recirculation mode. The effect of operating conditions such as electrical current, Fenton's reagent dosage, Fe(II) to H(2)O(2) molar ratio, and H(2)O(2) feeding time on the efficiency of E-Fenton process was investigated. It was found that E-Fenton method showed the synergetic effect on COD removal. The increase of Fenton's reagent dosage, Fe(II) to H(2)O(2) molar ratio, and the electrical current would lead to the increase of COD removal efficiency. Continuous addition of hydrogen peroxide was more effective than the addition of hydrogen peroxide in a single step and there existed an optimal H(2)O(2) feeding time for COD removal. The reaction system was modeled as a plug flow reactor (PFR) in series with a continuous stirred tank reactor (CSTR), and the pseudo-first order rate constant of COD removal was determined from the model based on the experimental data.     

Photocatalytic decomposition of 2-chlorophenol in aqueous solution by UV/TiO2 process with applied external bias voltage

The decomposition of 2-chlorophenol by UV/TiO2 process with the application of external bias voltage was examined in this study. Experiments were conducted in a batch reactor using TiO2-coated titanium sheet as anode and platinum sheet as cathode. The anode photocatalysis of 2-chlorophenol was totally inhibited for experiments conducted with the application of external anodic bias voltage lower than the flat band potential of TiO2. The decomposition rate of 2-chlorophenol was then increased with increasing external anodic bias voltage applied up to 0.0 V (versus SCE). The application of external bias voltage higher than 1.0 V did not markedly promote the photocatalysis of 2-chlorophenol possibly because the photocurrent induced was constant. Experimental results indicated that the decomposition of 2-chlorophenol was more effective for experiments conducted in acidic solutions due to the lower flat band potential of TiO2 and the higher photocurrent induced. The presence of electron scavengers in aqueous solution, such as oxygen molecules, may increase the decomposition rate of 2-chlorophenol. However, the effect of dissolved oxygen was diminished for experiments conducted with applied external bias voltage. The photocatalytic decomposition rate of 2-chlorophenol was enhanced linearly with the increasing UV light intensity when the external bias voltage was applied.     

Electrochemical treatment of anionic surfactants in synthetic wastewater with three-dimensional electrodes

The electrochemical oxidation of anionic surfactants (sodium dodecyl benzene sulfonate, DBS) contained in simulated wastewater treated by three-dimensional electrode system with combined modified kaolin served as packed bed particle electrodes and Ti/Co/SnO(2)-Sb(2)O(3) anode was studied, the chemical oxygen demand (COD) removal of pollutants in the solutions was also investigated. The results showed that the three-dimensional electrodes in combined process could effectively decompose anionic surfactants. The COD removal efficiency can reach 86%, much higher than that of Ti/Co/SnO(2)-Sb(2)O(3) electrodes used singly or modified kaolin employed singly (graphite as anode and cathode) on the same condition of pH 3 and 38.1 mA/cm(2) current density. The current efficiency and kinetic constant were calculated and energy consumption was studied. At the same time the influence of pH and current density on COD removal efficiency with combined three-dimensional electrodes was also investigated, respectively. The optimal initial pH value of degradation is 3 (acid condition), and a minor COD removal increase follows higher current density.     

Biosorption of 2,4-dichlorophenol from aqueous solution by Phanerochaete chrysosporium biomass: isotherms, kinetics and thermodynamics

The biosorption of 2,4-dichlorophenol (2,4-DCP) from aqueous solution on non-living mycelial pellets of Phanerochaete chrysosporium was studied with respect to pH, initial concentration of 2,4-DCP, temperature and pellet size. The fungal biomass exhibited the highest sorption capacity of 4.09 mg/g at an initial pH of 5.0, initial 2,4-DCP concentration of 50.48 mg/l, 25 degrees C and a pellet size of 1.0-1.5 mm in the investigated pH 2.0-11.0, initial concentrations of 5-50 mg/l, temperature 25-50 degrees C, and pellet size of 1.0-2.5 mm. The Freundlich model exhibited a slightly better fit to the biosorption data of 2,4-DCP than the Langmuir model. The biosorption of 2,4-DCP to biomass followed pseudo second-order adsorption kinetics. The second-order kinetic constants decreased with increasing temperature, and the apparent activation energy of biosorption was estimated to be -16.95 kJ/mol. The thermodynamic analysis indicates that the biosorption process was exothermic and that the adsorption of 2,4-DCP on P. chrysosporium might be physical in nature. Both intraparticle diffusion and kinetic resistances might affect the adsorption rate and that their relative effects varied with operation temperature in the biosorption of 2,4-DCP by mycelial pellets.     

Effects of Fe-doping on the photocatalytic activity of mesoporous TiO2 powders prepared by an ultrasonic method

Highly photoactive nanocrystalline mesoporous Fe-doped TiO(2) powders were prepared by the ultrasonic-induced hydrolysis reaction of tetrabutyl titanate (Ti(OC(4)H(9))(4)) in a ferric nitrate aqueous solution (pH 5) without using any templates or surfactants. The as-prepared samples were characterized by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), N(2) adsorption-desorption measurements, UV-visible adsorbance spectra (UV-vis) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities were evaluated by the photocatalytic oxidation of acetone in air. The results showed that all the Fe-doped TiO(2) samples prepared by ultrasonic methods were mesoporous nanocrystalline. A small amount of Fe(3+) ions in TiO(2) powders could obviously enhance their photocatalytic activity. The photocatalytic activity of Fe-doped TiO(2) powders prepared by this method and calcined at 400 degrees C exceeded that of Degussa P25 (P25) by a factor of more than two times at an optimal atomic ratio of Fe to Ti of 0.25. The high activities of the Fe-doped TiO(2) powders could be attributed to the results of the synergetic effects of Fe-doping, large BET specific surface area and small crystallite size.