Electrochemical degradation of phenol using electrodes of Ti/RuO(2)-Pt and Ti/IrO(2)-Pt

Electrochemical degradation of phenol was evaluated at two typical anodes, Ti/RuO(2)-Pt and Ti/IrO(2)-Pt, for being a treatment method in toxic aromatic compounds. The influences of current density, dosage of NaCl, initial phenol concentration on electrochemical phenol degradation were investigated. It was found that Ti/RuO(2)-Pt anode had a higher oxygen evolution potential than Ti/IrO(2)-Pt anode, which will increase the current efficiency for electrochemical degradation, and the instantaneous current efficiency (ICE) was relatively higher at the initial time during phenol electrolysis. HOCl formed during electrolysis would play an important role on the oxidation of phenol. For the Ti/RuO(2)-Pt anode, phenol concentration decreased from around 8mg/L to zero after 30min of electrolysis with 0.3g/L NaCl as supporting electrolyte at the current density of 10mA/cm(2). Although phenol could be completely electrochemical degraded at both Ti/RuO(2)-Pt and Ti/IrO(2)-Pt anodes, phenol degradation was slower at the Ti/IrO(2)-Pt anode than at the Ti/RuO(2)-Pt anode due to the fact that passivation was to be found at the Ti/IrO(2)-Pt anode.     

Electro-catalytic degradation of phenol on several metal-oxide anodes

Three kinds of Ti-based multilayer metal-oxide electrode, including Ti/SnO(2)+Sb(2)O(3)/PbO(2), Ti/SnO(2)+Sb(2)O(3)/MnO(x) and Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2) electrodes, were prepared by thermal decomposition, and SnO(2)+Sb(2)O(3) coatings were produced with a polymeric precursor method (PPM). The conversion of phenol was carried out with these electrodes as anodes under galvanostatic control. Samples during the electrolyses were characterized with UV-vis spectra and chromatography, and chemical oxygen demand (COD) and instantaneous current efficiency (ICE) for phenol degradation were also determined. The results show that phenol can be oxidized and degraded for all of the three anodes, and the oxidation reactions of phenol follow first-order kinetics, but there are considerable differences in the effectiveness and performance of electro-catalytic degradation. Phenol can be degraded relatively fast on the Ti/SnO(2)+Sb(2)O(3)/PbO(2) anode and the degradation rate of phenol is slower with the Ti/SnO(2)+Sb(2)O(3)/MnO(x) electrode, and the slowest with the Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2) electrode, whose apparent rate constants are 2.49 x 10(-2), 1.42 x 10(-2) and 9.76 x 10(-3) min(-1), respectively. The rates of electro-catalytic degradation relate to oxygen evolution potential, and the higher the oxygen evolution potential, the better the performance of electro-catalytic degradation. The potential for oxygen evolution at the Ti/SnO(2)+Sb(2)O(3)/PbO(2) anode is highest, then Ti/SnO(2)+Sb(2)O(3)/MnO(x), following Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2). The accelerated life tests at 60 degrees C and in 1.0 mol L(-1) aqueous H(2)SO(4) with an anodic current density of 4.0 Acm(-2) show that the service life is prolonged when the SnO(2)+Sb(2)O(3) interlayer coating are inserted between Ti substrate and active layers.     

涂层成分对IrO2（5）TiO2（60）Co3O4（x）RuO2（35—x）／Ti阳极材料析氯…

用电化学和Ｘ射线衍射方法研究了氧化物涂层成分热分解法制备的ＩｒＯ２（５）ＴｉＯ２（６０）Ｃｏ３Ｏ４（ｘ）ＲｕＯ２（３５－ｘ）／Ｔｉ阳极材料析氯速率的影响．ｘ值为０－１３ｍ／ｏ时，氧化物涂层为单相金红石型固溶体，阳极析氯速率随ｘ值增加，ｘ值大于１３ｍ／ｏ时，涂层中出现尖晶石Ｃｏ３Ｏ４第二相，析氯速率随ｘ值下降。     

涂层成分对IrO_2（5）TiO_2（60）Co_3O_4（x）RuO_2（35

用电化学和Ｘ射线衍射方法研究了氧化物涂层成分对热分解法制备的ＩｒＯ２（５）ＴｉＯ２（６０）Ｃｏ３Ｏ４（ｘ）ＲｕＯ２（３５—ｘ）／Ｔｉ阳极材料析氯速率的影响．ｘ值为０－１３ｍ／ｏ时，氧化物涂层为单相金红石型固溶体，阳极析氯速率随ｘ值增加，ｘ值大于１３ｍ／ｏ时，涂层中出现尖晶石Ｃｏ３Ｏ４第二相，析氯速率随ｘ值下降．     

Preparation and characterization of Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film as electrode material for the degradation of phenol

In this work, a novel electrode of titanium substrate coated with mixed metal oxides of SnO(2), Sb(2)O(3), Nb(2)O(5) and PbO(2) was successfully prepared using thermal decomposition and electrodeposition. The surface morphology and the structure of the prepared thin film were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. Experimental results showed that the structure of the prepared electrode might be described as a Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film and its surface was mainly comprised pyramidal-shape beta-PbO(2) crystals. The modified electrode had higher oxygen evolution potential than that of other PbO(2) modified electrodes. Electrocatalytic oxidation of phenol in aqueous solution was studied to evaluate the potential applications of this electrode in environmental science. The phenol removal efficiency in an artificial wastewater containing 0.50g/L phenol could reach 78.6% at 20 degrees C and pH 7.0 with an applied electricity density of 20mA/cm(2) and treatment time of 120min. When 21.3g/L chloride was added to this wastewater, the removal efficiency could reach to 97.2%.     

Simple and effective synthesis of methoxy-dimethylbenzene from electrochemical oxidation of p-xylene in methanol solvent catalyzed by SO(4)(2-)/ZrO(2)-M(x)O(y)

A series of composite solid superacid catalysts SO(4)(2-)/ZrO(2)-M(x)O(y) (M=Ti, Ni, Si) were prepared and investigated by means of Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). All catalysts exhibit good catalytic activity in the electrochemical reaction of p-xylene with methanol assisted with a pair of porous graphite plane electrodes and the selectivity of main products higher than 90% were observed. In particular, SO(4)(2-)/ZrO(2)-SiO(2) catalyst exhibited excellent catalytic activity. According to the experimental results, a possible free radical reaction mechanism confirmed by XPS and ultraviolet-visible (UV-vis) spectra was proposed. It may be concluded that a simple and feasible electrochemical catalytic oxidation reaction at room temperature and standard atmosphere may be possible.     

Schottky barrier mediated single-polarity resistive switching in Pt layer-included TiO(x) memory device

A distinct unipolar but single-polarity resistive switching behavior is observed in a TiO(x)/Pt/TiO(x) trilayer structure, formed by thermal oxidation of a Ti/Pt/Ti stack. As a comparison, a memory device with a single TiO(x) active layer (without addition of Pt midlayer) is also fabricated but it cannot perform resistive switching. Energy band diagrams are illustrated to realize the modulation of Schottky barrier junctions and current conduction in TiO(x)-based devices under various biasing polarities. Introduction of the Pt midlayer creates two additional Schottky barriers, which mediate the band bending potential at each metal-oxide interface and attains a rectifying current conduction at the high-resistance state. The rectifying conduction behavior is also observed with an AFM-tip as the top electrode, which implies the rectifying property is still valid when miniaturizing the device to nanometer scale. The current rectification consequently leads to a single-polarity, unipolar resistive switching and electrically rewritable performance for the TiO(x)/Pt/TiO(x) device.     

二组元（RuO2-TiO2）及三组元（RuO2-SnO2-TiO2）Ti阳极涂层的微观组织对其电化学性能的影响

通过热分解法制备了二组元（RuO₂-TiO₂）和三组元（RuO₂-SnO₂-TiO₂）Ti阳极涂层,并通过SEM、XRD以及电化学工作站对其结构及性能进行测试。结果表明：在烘干温度130 ℃,热氧化温度500 ℃,烧结时间15 min,退火时间1 h的条件下,所制备的三组元（RuO₂-SnO₂-TiO₂）Ti阳极涂层性能较为优异,析氯电位为1.128 V,析氧电位为1.674 V。在二组元（RuO₂-TiO₂）涂层中加入Sn组元,可以减少贵金属Ru的使用量,降低钛阳极涂层的成本;而且所形成的SnO₂可提高涂层表面的电催化活性,降低电极的析氯电位、析氧电位,延长电极的工作寿命。     

多元中间过渡层钛基氧化锰电极的寿命及电化学性能

采用热分解法制备了不同中间层的钛基氧化锰电极,利用SEM、XPS和XRD方法对电极进行了表征,应用加速寿命试验方法测试了电极在60℃、1.0mol/L H2SO4溶液中的预期使用寿命,同时测定了酸性溶液中该类电极的动力学参数(a、b、i0),运用双位垒模型讨论了电极的电化学性能。结果表明,具有RuO2+SnO2+MnO2+Sb2O4固溶体中间层的钛基氧化锰电极在高电流密度下(4A/cm2)的寿命可高达58h,电化学动力学表明该电极在酸性溶液中的析氧活化能较低,a值较小,i0值较大,是酸性溶液中较好的析氧电极材料。     

Experimental design methodology applied to electrochemical oxidation of the herbicide atrazine using Ti/IrO(2) and Ti/SnO(2) circular anode electrodes

The degradation of the herbicide atrazine in aqueous medium (initial concentration of 100 μg l(-1)) has been studied by electrooxidation process using Ti/IrO(2) and Ti/SnO(2) circular anode electrodes. The performance of the electrolytic cell resulted from its capability of reacting on the pollutants by using indirect effect of electrical current where active chlorine is electrochemically generated. A factorial experimental design was firstly used for determining the influent parameters on the herbicide atrazine degradation. The current intensity and treatment time were the main influent parameters on the degradation rate. Using a 2(4) factorial matrix, the best performance for atrazine degradation (removal of 95%) was obtained by selecting Ti/IrO(2) anode operated at a current intensity of 2.0 A during 40 min of treatment time in the presence of 1.0 g Na Cl l(-1). Then, the optimal experimental parameters for atrazine degradation have been investigated by using a Central Composite methodology. Under the optimal conditions determined by this method, electrooxidation can economically be applied to oxidise atrazine (73% of degradation for a total cost of 0.057 US$m(-3)) while using Ti/IrO(2) anode operated at a current intensity of 1.4A during 22 min of treatment time in the presence of 1.0 g NaCl l(-1).     

Development of a high performance electrochemical wastewater treatment system

In order to construct a high performance electrochemical system for practical use in industrial and municipal wastewater treatment, laboratory scale electrochemical experiments were performed to select anode materials by applying pulse voltage. Based on the results obtained from laboratory experiments, a pilot plant of electrochemical treatment system (0.3 m3 h(-1)) was successfully developed, in which electrocoagulation and electrooxidation processes were used. The performance of the treatment system was evaluated by treating domestic wastewater, pond water containing algae and wastewater from hog raising. As a result, production of hydroxyl radicals detected with p-nitrosodimethylaniline (RNO) at Ti/RuO(2)-TiO(2) anode was larger than with a platinum anode, and hydroxyl radicals were not detected at Ti anode. Moreover, a significant difference in electrocatalytic properties for ammonia oxidation between platinum and Ti/RuO(2)-TiO(2) electrodes was not observed from the cyclic voltammogram. The removal of T-N, T-P, NH(4)-N and COD from domestic wastewater and pond water containing algae was approximately 90%, while the removal of chlorophyll-a (chl-a) of algae was approximately 100%. Although the electrochemical treatment system was effective on biologically treated wastewater from hog raising, the treatment of raw wastewater was not remarkable. Therefore, the electrochemical treatment system requires pretreatment when used with wastewater containing high concentrations of suspended solids.     

Synthesis and characterization of CuO/Ce 1-x Ti x O2 catalysts used for low-temperature CO oxidation

A series of CuO/Ce(1-x)Ti(x)O(2) catalysts used for low-temperature CO oxidation were prepared by impregnation with the support derived from surfactant-assisted co-precipitation. The techniques of N(2) adsorption/desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction by H(2) (H(2)-TPR) were employed for catalyst characterization. It is found that the support CeO(2) prepared by the surfactant-assisted method possesses much larger specific surface area than the one obtained from conventional precipitation. Doping Ti in the support with Ti/Ce atomic ratio of 1:9 or 3:7 can further increase the surface area of CeO(2) and decrease its crystallite size. As a result, the active Cu species possess higher dispersion on the support Ce(1-x)Ti(x)O(2) than on pure CeO(2). The strong interaction between the dispersed Cu species and the support Ce(1-x)Ti(x)O(2) makes the catalysts possess much higher oxidation activity and thermal stability. However, when the ratio of Ti/Ce reaches 5:5, opposite effect is found, due to the highest surface concentration of Ti and the lack of surface highly dispersed copper species.     

Electrochemical degradation of polycyclic aromatic hydrocarbons in creosote solution using ruthenium oxide on titanium expanded mesh anode

In this study, expanded titanium (Ti) covered with ruthenium oxide (RuO(2)) electrode was used to anodically oxidize polycyclic aromatic hydrocarbons (PAH) in creosote solution. Synthetic creosote-oily solution (COS) was prepared with distilled water and a commercial creosote solution in the presence of an amphoteric surfactant; Cocamidopropylhydroxysultaine (CAS). Electrolysis was carried out using a parallelepipedic electrolytic 1.5-L cell containing five anodes (Ti/RuO(2)) and five cathodes (stainless steel, 316 L) alternated in the electrode pack. The effects of initial pH, temperature, retention time, supporting electrolyte, current density and initial PAH concentration on the process performance were examined. Experimental results revealed that a current density of 9.23 mA cm(-2) was beneficial for PAH oxidation. The sum of PAH concentrations for 16 PAHs could be optimally diminished up to 80-82% while imposing a residence time in the electrolysis cell of 90 min. There was not a significant effect of the electrolyte (Na(2)SO(4)) concentration on oxidation efficiency in the investigated range of 500-4000 mg/L. However, an addition of 500 mg Na(2)SO(4)L(-1) was required to reduce the energy consumption and the treatment cost. Besides, there was no effect of initial PAH concentration on oxidation efficiency in the investigated range of 270-540 mg PAHL(-1). Alkaline media was not favourable for PAH oxidation, whereas high performance of PAH degradation could be recorded without initial pH adjustment (original pH around 6.0). Likewise, under optimal conditions, 84% of petroleum hydrocarbon (C(10)-C(50)) was removed, whereas removal yields of 69% and 62% have been measured for O&G and COD, respectively. Microtox and Daphnia biotests showed that electrochemical oxidation using Ti/RuO(2) could be efficiently used to reduce more than 90% of the COS toxicity.     

Ammonia removal in electrochemical oxidation: mechanism and pseudo-kinetics

This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO(2)/Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl(-). The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L(-1)h(-1) and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl(-). About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N(2) in the produced gas. The rate at which Cl(-) lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl(-) concentration affected the constant of the pseudo zero-order kinetics, expressed by k=0.0024[Cl(-)]xj. The ammonia was reduced to less than 0.5 mg N L(-1) after 2h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements.     

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.     

Oxalic acid mineralization by electrochemical oxidation processes

In this study, two electrochemical oxidation processes were utilized to mineralize oxalic acid which was a major intermediate compound in the oxidation of phenols and other aromatic compounds. The anode rod and cathode net were made of a titanium coated with RuO(2)/IrO(2) (Ti-DSA) and stainless steel (S.S. net, SUS304), respectively. First, the Fered-Fenton process, which used H(2)O(2) and Fe(2+) as additive reagents, achieved 85% of TOC removal. It proceeded with ligand-to-metal charge-transfer (LMCT), which was evidenced by the accumulation of metallic foil on the selected cathode. However, in the absence of H(2)O(2)/Fe(2+), it showed a higher TOC removal efficiency while using Cl(-) only as an additive reagent due to the formation of hypochlorite on the anode. It was also found that the mineralization of oxalic acid by electrolysis generated hypochlorite better than the dosage of commercial hypochlorite without electricity. Also, pH value was a major factor that affected the mineralization efficiency of the oxalic acid due to the chlorine chemistry. 99% TOC removal could be obtained by Cl(-) electrolysis in an acidic environment.     

Electrochemical oxidation of a textile dye wastewater using a Pt/Ti electrode

Textile dye wastewater (TDW) from a reactive azo dyeing process was treated by an electrochemical oxidation method using Ti/Pt as anode and stainless steel 304 as cathode. Due to the strong oxidizing potential of the chemicals produced (chlorine, oxygen, hydroxyl radicals and other oxidants) when the wastewater was passed through the electrolytic cell the organic pollutants were oxidized to carbon dioxide and water. A number of experiments were run in a batch, laboratory-scale, pilot-plant, and the results are reported here according to residence time and initial addition of HCl in raw wastewater. When of 2 ml of HCl 36% were added and after 18 min of electrolysis at 0.89 A/cm(2), chemical oxygen demand (COD) was reduced by 86%, biochemical oxygen demand (BOD(5)) was reduced by 71%, ADMI color units were reduced by 100%, and TKN was reduced by 35%. The biodegradability of the wastewater was improved because the COD/BOD ratio decreased from 2.16 to 1.52. At the same time the efficiency of the electrode was about 170 g h(-1) A(-1) m(-2). and the mean energy consumption was 21 kW h/kg of COD. These results indicate that this electrolytic method could be used for effective TDW oxidation or as a feasible detoxification and color removal pretreatment stage for biological post treatment.     

Catalytic oxidation of anionic surfactants by electrochemical oxidation with CuO-Co2O3-PO4(3-) modified kaolin

A new catalytic oxidation of anionic surfactants by electrochemistry method was designed and used to investigate the removal of anionic surfactant from simulated wastewater. Synergetic effect on COD removal was studied when integrating the electrochemical reactor, using porous graphite as anode and cathode, with the effective CuO-Co2O3-PO4(3-) modified kaolin catalyst in a single undivided cell. The result showed that this combined process could effectively remove anionic surfactant. Its COD removal efficiency was much higher than those individual processes and could reach up to 90% in 60 min. The operating parameters such as initial pH, cell voltage, and current intensity were also investigated. Possible theory for COD removal was also proposed to predict the role of modified kaolin, electro-catalysis and oxidation in the combined process. The pollutants in wastewater could be decreased by the high reactive OH* that produced on the surface of catalyst by the decomposition of electrochemical generated H2O2. The result indicates that the catalytic oxidation by electrochemistry method is a promising wastewater treatment technique.     

MnOx/AC的制备及电催化氧化降解苯酚

采用活性炭还原KMnO4制备MnOx/AC催化剂,利用SEM、XPS对其进行表征。结果表明,Mn以MnO2的形式存在于活性炭表面。辊压成型法制成MnOx/AC电极,以所制MnOx/AC电极为阴极、Ti/RuO2电极为阳极,对苯酚废水进行电解氧化处理,研究了电流密度、电极间距离、初始pH值、电解质溶液浓度等因素对处理效果...     

Electrochemical treatment of Procion Black 5B using cylindrical flow reactor--a pilot plant study

The paper presents the results of an efficient electrochemical treatment of Procion Black 5B--a pilot plant study. Experiments were conducted at different current densities and selected electrolyte medium using Ti/RuO2 as anode, stainless-steel as cathode in a cylindrical flow reactor. By cyclic voltammetric analysis, the best condition for maximum redox reaction rate was found to be in NaCl medium. During the various stages of electrolysis, parameters such as COD, colour, FTIR, UV-vis spectra studies, energy consumption and mass transfer coefficient were computed and presented. The experimental results showed that the electrochemical oxidation process could effectively remove colour and the chemical oxygen demand (COD) from the synthetic dye effluent. The maximum COD reduction and colour removal efficiencies were 74.05% and 100%, respectively. Probable theory, reaction mechanism and modeling were proposed for the oxidation of dye effluent. The results obtained reveal the feasibilities of application of electrochemical treatment for the degradation of Procion Black 5B.