Arsenic removal from groundwater using low-cost carbon composite electrodes for capacitive deionization.

Affordable carbon composite electrodes were developed to treat low-concentrated groundwater using capacitive deionization (CDI). A carbon slurry prepared using activated carbon powder (ACP), poly(vinylidene fluoride), and N-methyl-2-pyrrolidone was employed as a casting solution to soak in a low-cost porous substrate. The surface morphology of the carbon composite electrodes was investigated using a video microscope and scanning electron microscopy. The capacitance and electrical conductivity of the carbon composite electrodes were then examined using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. According to the CV and EIS measurements, the capacitances and electrical conductivities of the carbon composite electrodes were in the range of 8.35-63.41 F g(-1) and 0.298-0.401 S cm(-1), respectively, depending on ACP contents. A CDI cell was assembled with the carbon composite electrodes instead of with electrodes and current collectors. The arsenate removal test included an investigation of the optimization of several important operating parameters, such as applied voltage and solution pH, and it achieved 98.8% removal efficiency using a 1 mg L(-1) arsenate solution at a voltage of 2 V and under a pH 9 condition.

Morphologically Aligned Cation-Exchange Membranes by a Pulsed Electric Field for Reverse Electrodialysis.

A low-resistance ion-exchange membrane is essential to achieve the high-performance energy conversion or storage systems. The formation methods for low-resistance membranes are various; one of the methods is the ion channel alignment of an ion-exchange membrane under a direct current (DC) electric field. In this study, we suggest a more effective alignment method than the process with the DC electric field. First, an ion-exchange membrane was prepared under a pulsed electric field [alternating current (AC) mode] to enhance the effectiveness of the alignment. The membrane properties and the performance in reverse electrodialysis (RED) were then examined to assess the membrane resistance and ion selectivity. The results show that the membrane electrical resistance (MER) had a lower value of 0.86 Ω cm(2) for the AC membrane than 2.13 Ω cm(2) observed for the DC membrane and 4.30 Ω cm(2) observed for the pristine membrane. Furthermore, RED achieved 1.34 W/m(2) of maximum power density for the AC membrane, whereas that for the DC membrane was found to be 1.14 W/m(2) [a RED stack assembled with CMX, used as a commercial cation-exchange membrane (CEM), showed 1.07 W/m(2)]. Thereby, the novel preparation process for a remarkable low-resistance membrane with high ion selectivity was demonstrated.

Designing a Highly Active Metal-Free Oxygen Reduction Catalyst in Membrane Electrode Assemblies for Alkaline Fuel Cells: Effects of Pore Size and Doping-Site Position.

To promote the oxygen reduction reaction of metal-free catalysts, the introduction of porous structure is considered as a desirable approach because the structure can enhance mass transport and host many catalytic active sites. However, most of the previous studies reported only half-cell characterization; therefore, studies on membrane electrode assembly (MEA) are still insufficient. Furthermore, the effect of doping-site position in the structure has not been investigated. Here, we report the synthesis of highly active metal-free catalysts in MEAs by controlling pore size and doping-site position. Both influence the accessibility of reactants to doping sites, which affects utilization of doping sites and mass-transport properties. Finally, an N,P-codoped ordered mesoporous carbon with a large pore size and precisely controlled doping-site position showed a remarkable on-set potential and produced 70% of the maximum power density obtained using Pt/C.

Isoindigo-based small molecules for high-performance solution-processed organic photovoltaic devices: the electron donating effect of the donor group on photo-physical properties and device performance.

Five solution processable isoindigo-based donor-acceptor-donor (D-A-D) small molecules with different electron donating strengths have been designed and synthesized. The variation in the electron donating strength of the donor group strongly affected the optical, thermal, electrochemical and photovoltaic device performances of the isoindigo organic materials. The highest power conversion efficiency of ~3.2% was achieved in the bulk heterojunction photovoltaic device consisting of ID3T as the donor and PC70BM as the acceptor. This work demonstrates the potential of isoindigo moieties as electron-deficient units and presents guidelines for the synthesis of D-A-D small molecules for producing highly efficient, solution-processed organic photovoltaic devices.

Analyses of interfacial resistances in a membrane-electrode assembly for a proton exchange membrane fuel cell using symmetrical impedance spectroscopy.

Interfacial resistances between the polymer electrolyte membrane (PEM) and catalyst layer (CL) in membrane-electrode assemblies (MEAs) have yet to be systematically examined in spite of its great importance on the fuel cell performance. In order to investigate ionic transport through the PEM/CL interface, the symmetrical impedance mode (SIM) was employed in which the same type of gas was injected (H(2)/H(2)). In this study, the ionic transport resistance at the interface was controlled by the additionally sprayed outer ionomer on the surface of each CL. Effectiveness of the outer ionomer on ionic transport at the interface was quantitatively explained by the reduced contact, proton hydration, and charge transport resistances in the SIM. To characterize the ionic transport resistance, the concept of total resistance (R(tot)) in the SIM was introduced, representing the overall ohmic loss due to proton transport in an MEA. This concept was successfully supported via an agreement of the interpretation and the linear correlation that was obtained between the admittance (1/R(tot)) and the performance of a fuel cell in the ohmic loss region. This correlation will enable researchers to predict the performance of a fuel cell under the influence of proton transport by examining the R(tot) in the SIM.

Fabrication of a composite anion exchange membrane with aligned ion channels for a high-performance non-aqueous vanadium redox flow battery.

Fabrication of high-conductivity ion exchange membranes (IEMs) is crucial to improve the performance of non-aqueous vanadium redox flow batteries (NAVRFBs). In the present work, anion exchange membranes with high-conductivity were fabricated by aligning ion channels of the polymer electrolyte impregnated in porous polytetrafluoroethylene (PTFE) under electric fields. It was observed that the ion channels of the polymer electrolyte were uniformly orientated in the atomic-force microscopy image. Its morphological change could minimize detouring of the transport of BF4 - ions. The results showed through-plane conductivity was improved from 12.7 to 33.1 mS cm-1. The dimensional properties of the fabricated membranes were also enhanced compared with its cast membrane owing to the reinforcing effect of the substrate. Especially, the NAVRFB assembled with the optimized membrane showed increased capacities, with a 97% coulombic efficiency and 70% energy efficiency at 80 mA cm-2. Furthermore, the optimized membrane made it possible to operate the NAVRFB at 120 mA cm-2. Its operating current density was 120 times higher than that of a frequently used AHA membrane for RFBs.

Hydrogen bonding: a channel for protons to transfer through acid-base pairs.

Different from H(3)O(+) transport as in the vehicle mechanism, protons find another channel to transfer through the poorly hydrophilic interlayers in a hydrated multiphase membrane. This membrane was prepared from poly(phthalazinone ether sulfone kentone) (SPPESK) and H(+)-form perfluorosulfonic resin (FSP), and poorly hydrophilic electrostatically interacted acid-base pairs constitute the interlayer between two hydrophilic phases (FSP and SPPESK). By hydrogen bonds forming and breaking between acid-base pairs and water molecules, protons transport directly through these poorly hydrophilic zones. The multiphase membrane, due to this unique transfer mechanism, exhibits better electrochemical performances during fuel cell tests than those of pure FSP and Nafion-112 membranes: 0.09-0.12 S cm(-1) of proton conductivity at 25 degrees C and 990 mW cm(-2) of the maximum power density at a current density of 2600 mA cm(-2) and a cell voltage of 0.38 V.

Detoxification of simulated textile wastewater using a membraneless electrochemical reactor with immobilized peroxidase.

Simulated textile wastewater was degraded using a membraneless electrochemical reactor with immobilized peroxidase on the porous Celite. The optimal current density was 10 A m(-2), at which the highest amount of hydrogen (H(2)O(2)) could be generated. The decolorization efficiencies of the simulated wastewater using the electrochemical and electroenzymatic methods were 35% and 92%, respectively. Biodegradability, the ratio of 5-day biochemical oxygen demand to chemical oxygen demand (BOD(5)/COD), was enhanced about 1.88 times when using the electroenzymatic treatment rather than raw wastewater, which could not be achieved by the electrochemical treatment. The toxic unit (TU), calculated using the lethal concentration (LC(50)) of Daphnia magna (D. Magna), of effluent treated by electroenzymatic method was below 1, whereas those of simulated textile wastewater and effluent treated by electrochemical method were 11.4 and 3.9, respectively.

Optimized coverage of gold nanoparticles at tyrosinase electrode for measurement of a pesticide in various water samples.

Gold nanoparticles (AuNPs) were electrodeposited onto a glassy carbon (GC) electrode to increase the sensitivity of the tyrosinase (TYR) electrode. By controlling the applied potential and time, the coverage of AuNPs at the TYR electrode was optimized with respect to the current response. The voltammetric measurements revealed a sensitive enzymatic oxidation and electrochemical reduction of substrate (phenol and catechol). The quantitative relationships between the inhibition percentage and the pesticide concentration in various water samples were measured at the TYR-AuNP-GC electrode, showing an enhanced performance attributed by the use of AuNPs.

Control of the fixed charge distribution in an ion-exchange membrane via diffusion and the reaction rate of the monomer.

The fixed charge distribution of the ion-exchange membranes was controlled by introducing ion-exchangeable groups onto the glycidyl methacrylate (GMA)-g-polypropylene (PP) membranes. The membranes were prepared by plasma-induced graft polymerization with uniform or nonuniform graft distributions over the cross section. The effects of reaction conditions on the graft distribution in plasma-induced graft polymerization were investigated to obtain the GMA-g-PP membranes with different graft distributions. The examined reaction conditions were plasma power, gas pressure of the plasma, solvent, concentration of the monomer solution, and reaction temperature. The graft distribution of the membranes was directly observed by a microscopic Fourier transform infrared mapping method and field-emission scanning electron microscopy. Also, the graft distribution was correlated with the relative magnitude of the reaction rate to the diffusion rate, which may determine the grafting yield as a function of the distance from the surface. A high rate of diffusion compared to the reaction rate resulted in a more uniform graft distribution. Among the grafting conditions, control of the reaction temperature was found to be the most effective for selectively preparing both uniform and nonuniform graft distribution. Uniform graft distribution was achieved when the reaction was conducted at 1 degrees C because of the relatively rapid diffusion and the slow reaction of the monomer, while nonuniform graft distribution occurred at higher reaction temperatures. Consequently, uniformly and nonuniformly charged cation-exchange membranes were prepared through sulfonation of the corresponding GMA-g-PP membranes at temperatures of 1 and 40 degrees C, respectively.

An electrical impedance spectroscopic (EIS) study on transport characteristics of ion-exchange membrane systems.

This study aimed at investigating ion-exchange membrane systems using impedance spectroscopy. Nyquist plots showed that the impedance obtained in this study described the ion-exchange membrane system well, as consisting of (i) an ion-exchange membrane immersed in solution, (ii) electrical double layers at the membrane surface, and (iii) diffusion boundary layers arising from the interface between the ion-exchange membrane and the electrolyte solutions. Taking into account the physical and electrochemical understanding of the ion-exchange membrane system, an equivalent circuit was suggested to quantitatively analyze each component of the ion-exchange membrane system. To confirm the reliability of the proposed equivalent circuit, the resistance and capacitance were estimated from the impedance data and the values were compared with other experimental results (e.g., I-V curves). The comparison showed good agreement and validated the equivalent circuit. Moreover, the impedance measurements made it possible to confirm the electroconvective effects in the over LCD region.

An approach to fouling characterization of an ion-exchange membrane using current-voltage relation and electrical impedance spectroscopy.

Fouling phenomena of an anion-exchange membrane by bovine serum albumin (BSA) were investigated using current-voltage relation and electrical impedance spectroscopy (EIS) in this study. Electrochemical parameters of the Neosepta CMX cation- and AMX anion-exchange membrane (Tokuyama Corp., Japan) such as limiting current density (LCD), transport number, plateau length, and fraction of the conducting phase were measured. Fraction of the conducting phase of the ion-exchange membranes, calculated from the modified Sand equation, played an important role in determining the electrochemical parameters in the presence of foulants such as BSA. Fraction of the conducting phase of the AMX membrane significantly decreased in the presence of BSA. Two distinguishable slopes were observed in the over-LCD region of the current-voltage (I-V) curve, indicating the change of resistance. To further elucidate the phenomena, the electrical impedance spectroscopic study was carried out using the offset alternating current. It was found that the negatively charged loose fouling layer changed to the dense deposited BSA on the surface of the AMX membrane occurring along with enhanced water dissociation phenomena at the surface of the fouled AMX membrane at a higher current density. This result was confirmed by water dissociation experiments in a six-compartment electrodialysis cell.

Enhancement of electrodialysis performances using pulsing electric fields during extended period operation.

Many methods have been considered for mitigating and minimizing fouling potentials in the electrodialysis process, because fouling of ion exchange membranes is one of the significant considerations in process design and operation. In the observation of foulant behaviors, it was observed that the humate was deposited and formed a loosely packed fouling layer on the anion-exchange membrane surfaces, thus having reversible fouling effects on the process. In order to investigate the effects of the frequencies on the electrodialysis performance during fouling experiments in the presence of humate, the square-wave powers having various frequencies in the electric fields were employed. The results showed that the pulsing electric fields mitigated the fouling potential and that there exists an optimal frequency for the minimization of the fouling potential. Also, the pulsation of the electric field with an optimal frequency reduced the fouling potential of the already fouled membrane systems in the continuous batch runs. It was suggested that the electric field with pulsing effects enhanced the electrophoretic mobilities of the charged foulants, thus decreasing fouling potentials.

Biodegradation and detoxification of organophosphate insecticide, malathion by Fusarium oxysporum f. sp. pisi cutinase.

Efficiencies of two lypolytic enzymes (fungal cutinase and yeast esterase) in malathion degradation were investigated. Surprisingly, degradation rate of malathion by fungal cutinase was very high, i.e. almost 60% of initial malathion (500 mg l(-1)) was decomposed within 0.5 h, and nearly 50% of the degraded malathion disappeared within initial 15 min. With the yeast esterase, despite the same concentration, more than 65% of malathion remained even after 2-day treatment. During enzymatic degradation of malathion, two malathion-derived compounds were detected, and time-course changes in composition were also monitored. In the degradation by both fungal cutinase and yeast esterase, two additional organic chemicals were produced from malathion: malathion monoacid (MMA) and malathion diacid (MDA) by ester hydrolysis. Final chemical composition after 2 d was significantly dependent on the enzyme used. Fungal cutinase produced MDA as a major degradation compound. However in the malathion degradation by yeast esterase, an isomer of MMA was produced in abundance in addition to MDA. Toxic effects of malathion and its final degradation products were investigated using various recombinant bioluminescent bacteria. As a result, the degradation products (including MMA) by esterase severely caused membrane damage and inhibition of protein synthesis in bacterial cells, while in the fungal cutinase processes, malathion was significantly degraded to non-toxic MDA after the extended period (2 days).

Electroenzymatic degradation of azo dye using an immobilized peroxidase enzyme.

Azo dyes are largely resistant to biodegradation and persist in conventional wastewater treatment processes. Combining enzymatic catalysis and the electrochemical generation of hydrogen peroxide (H2O2), an electroenzymatic process was developed, which is a potential alternative to traditional processes. In this study, an electroenzymatic method that uses an immobilized horseradish peroxidase enzyme (HRP), was investigated to degrade orange II (azo dye) within a two-compartment packed-bed flow reactor. To evaluate the electroenzymatic degradation of orange II, electrolytic experiments were carried out with 0.42 U/mL HRP at -0.5 V. It was found that removal of orange II was partly due to its adsorption to the graphite felt. The overall application of the electroenzymatic led to a greater degradation rate than the use of electrolysis alone. Also the by-products formed were found to consist primarily of an aromatic amine, sulfanilic acid, and unknown compounds.

Electroenzymatic oxidation of veratryl alcohol by lignin peroxidase.

This paper reports the formation of veratraldehyde by electroenzymatic oxidation of veratryl alcohol (3,4-dimethoxybenzyl alcohol) hybridizing both electrochemical and enzymatic reactions and using lignin peroxidase. The novel electroenzymatic method was found to be effective for replacement of hydrogen peroxide by an electrochemical reactor, which is essential for enzyme activity of lignin peroxidase. The effects of operating parameters such as enzyme dosage, pH, and electric potential were investigated. Further, the kinetics of veratryl alcohol oxidation in an electrochemical reactor were compared to oxidation when hydrogen peroxide was supplied externally.

Kinetics of adsorption of Co(II) removal from water and wastewater by ion exchange resins.

The capacity of ion exchange resins, IRN77 and SKN1, for removal of cobalt from aqueous solution has been investigated under different conditions namely initial solution pH, initial metal-ion concentration, and contact time. The equilibrium data obtained in this study have been found to fit both the Langmuir and Freundlich adsorption isotherms. The adsorption of Co(II) on these resins follows first-order reversible kinetics. The film diffusion of Co(II) in these ion exchange resins was shown to be the main rate limiting step. The studies showed that these cation exchange resins can be used as efficient adsorbent material for the removal of Co(II) from aqueous solutions.

A study on stack configuration of continuous electrodeionization for removal of heavy metal ions from the primary coolant of a nuclear power plant.

This study investigated the production of high-purity water in the primary coolant of a nuclear power plant via the continuous electrodeionization (CEDI) process, using ion exchange resins as ion-conducting media between ion exchange membranes. The effectiveness of this method was examined with respect to the removal of heavy metals. The study was carried out on a laboratory scale with an effective area of 20 cm(2). The CEDI system was operated with a layered bed of cation exchange resins, anion exchange resins, and mixed-bed ion exchange resins. The stack configuration was designed to prevent a reaction between metal ions and hydroxide ions. The CEDI operation with the layered bed removed more than 99% of the ions at 30% of the current efficiency. The results showed that, with an inlet conductivity of 40 microScm(-1), a linear velocity of 4.17 cms(-1), and an applied current density of 17 mAcm(-2), the CEDI process yielded an outlet conductivity of 0.5 microScm(-1), thereby preventing the precipitation of metal ions. This study therefore successfully demonstrated the feasibility of the CEDI operation for the removal of heavy metals at a very low concentration.

Degradation of 2,4,6-trinitrotoluene by immobilized horseradish peroxidase and electrogenerated peroxide.

This paper presents horseradish peroxidase (HRP)-catalyzed removal of 2,4,6-trinitrotoluene (TNT) by an electrochemical packed-bed flow reactor operated in a circulating batch mode with the help of in situ generated hydrogen peroxide. HRP immobilized on the reticulated vitreous carbon electrode was prepared for the cyclic voltammetry of 2,4,6-TNT. Effects of pH and temperature on the TNT electroreduction in 0.2M phosphate buffer saturated with oxygen were examined. HRP immobilized carbon electrode was capable of catalyzing the oxidation and detoxification of 44 microM TNT in aqueous solution under optimized conditions. The removal rate of TNT for the electroenzymatic method was much greater than for electrochemical and biochemical methods. Stoichiometric and kinetic studies indicated that the hydrogen peroxide was utilized more effectively in the electroenzymatic method. Denitrification as intermediate reaction was also investigated.

Recovery of ammonium sulfate from fermentation waste by electrodialysis.

Electrodialysis experiments of the lysine fermentation waste were performed to generate demineralized feed and ammonium sulfate, which can be utilized as a fertilizer and an animal feed, respectively. The electrodialysis performances were compared for different ion exchange membranes in terms of ammonium sulfate removal rate, resistance and conductivity change. Analysis of fouling phenomena revealed that organics fouled ion exchange membranes reversibly in electrodialysis of the fermentation waste. In this study, mitigation of membrane fouling with the pulsed electric field was examined for the electrodialysis of the fermentation waste containing strong foulants. The half-wave power reduced membrane fouling significantly. For a quantitative measure of the membrane fouling tendency, a membrane fouling index for electrodialysis was used. This study showed the potential use of pulsed power as an effective fouling mitigation method for the electrodialysis of fermentation waste.