Electrochemical reduction of carbon dioxide in an MFC-MEC system with a layer-by-layer self-assembly carbon nanotube/cobalt phthalocyanine modified electrode

Electrochemical reduction of carbon dioxide (CO(2)) to useful chemical materials is of great significance to the virtuous cycle of CO(2). However, some problems such as high overpotential, high applied voltage, and high energy consumption exist in the course of the conventional electrochemical reduction process. This study presents a new CO(2) reduction technique for targeted production of formic acid in a microbial electrolysis cell (MEC) driven by a microbial fuel cell (MFC). The multiwalled carbon nanotubes (MWCNT) and cobalt tetra-amino phthalocyanine (CoTAPc) composite modified electrode was fabricated by the layer-by-layer (LBL) self-assembly technique. The new electrodes significantly decreased the overpotential of CO(2) reduction, and as cathode successfully reduced CO(2) to formic acid (production rate of up to 21.0 ± 0.2 mg·L(-1)·h(-1)) in an MEC driven by a single MFC. Compared with the electrode modified by CoTAPc alone, the MWCNT/CoTAPc composite modified electrode could increase the current and formic acid production rate by approximately 20% and 100%, respectively. The Faraday efficiency for formic acid production depended on the cathode potential. The MWCNT/CoTAPc composite electrode reached the maximum Faraday efficiency at the cathode potential of ca. -0.5 V vs Ag/AgCl. Increasing the number of electrode modification layers favored the current and formic acid production rate. The production of formic acid was stable in the MFC-MEC system after multiple batches of CO(2) electrolysis, and no significant change was observed on the performances of the modified electrode. The coupling of the catalytic electrode and the bioelectrochemical system realized the targeted reduction of CO(2) in the absence of external energy input, providing a new way for CO(2) capture and conversion.     

Degradation of methylparathion in aqueous solution by electrochemical oxidation

The electrochemical degradation of methylparathion has been investigated by using Ti/Pt as anode, Stainless Steel 304 as cathode, and sodium chloride as electrolyte. The pesticide is rapidly degraded, but full mineralization is not observed. Degradation products have been monitored through gas chromatography and mass spectrometry, and the overall degradation process has been monitored through dissolved and particulate organic carbon, sulfur, and phosphorus measurements. Several intermediates have been identified, and oxalic, formic, and acetic acids as well as tetraphosphorus trisulfide have been recognized as final products of the degradation process. A proposed mechanism of the process is presented.     

Electrolytic methanogenic-methanotrophic coupling for tetrachloroethylene bioremediation: proof of concept

Coupling of methanogenic and methanotrophic catabolisms was performed in a single-stage technology equipped with a water electrolysis cell placed in the effluent recirculation loop. The electrolysis-generated hydrogen served as an electron donor for both bicarbonate reduction into CH4 and reductive dechlorination, while the O2 and CH4, supported the cometabolic oxidation of chlorinated intermediates left over by the tetrachloroethylene (PCE) transformation. The electrolytical methanogenic/methanotrophic coupled (eMaMoC) process was tested in a laboratory-scale setup at PCE loads ranging from 5 to 50 micromol/L(rx) x d (inlet concentrations from 4 to 11 mg/L), and at various hydraulic residence times (HRT). Degradation followed essentially a reductive dechlorination pathway from PCE to cis-1,2-dichloroethene (DCE), and an oxidative pathway from DCE to CO2. PCE reductive dechlorination to DCE was consistently over 98% while a maximum oxidative DCE mineralization of 89% was obtained at a load of 4.3 micromol PCE/ L(rx) x d and an HRT of 6 days. Controlling dissolved oxygen concentrations within a relatively low range (2-3 mg/L) seemed instrumental to sustain the overall degradation capacity. Degradation kinetics were further evaluated: the apparent half-saturation constant (K(s)) had to be set relatively high (29 microM) for the simulated data to best fit the experimental ones. In spite of such kinetic limitations, the eMaMoC system, while fueled by water electrolysis, was effective in building and sustaining a functional methanogenic/methanotrophic consortium capable of significant PCE mineralization in a single-stage process. Hence, degradation standards are within reach so long as the methanotrophic DCE-oxidizing potential, including substrate affinity, are optimized and HRT accordingly adjusted.     

Photocatalytic degradation and mineralization of commercial methamidophos in aqueous titania suspension

The photocatalytic degradation of a commercial methamidophos (MAP) emulsion in aqueous suspension containing mesoporous titania (m-TiO2) nanoparticles under UV irradiation was investigated. The mineralization rate of MAP went up steadily as prolonging the irradiation time and reached ca. 95% after 4 h irradiation based on determination of the end-products (NO3-, PO4(3-), and SO4(2-)) of MAP through IC analysis. Moreover, the degradation kinetics of MAP followed the first-order reaction and has been monitored through GC-PFPD analysis, which also showed that MAP and the organic solvent as well as additive in the pesticide emulsion can be degraded readily and simultaneously. Photodegradation intermediates derived from two different concentrations of MAP were detected by GC-MS technique. The experimental facts indicated that the photodegradation mechanism of MAP mainly involves electron transfer process and hydroxylation process, and the dominant mechanism for MAP degradation in the initial steps can be attributed to the electron transfer process, which resulted in the formation of all intermediates containing P species detected in the initial photodegradation stage.     

Dual electrodes oxidation of dye wastewater with gas diffusion cathode

The high energy cost of an electrochemical method is the fatal drawback that hinders its large scale application in wastewater treatment. In traditional single-chamber electrolysis cell, only direct oxidation at an anode exists. Although a small amount of hydrogen peroxide is produced at the cathode by reduction, it is transferred to the anode and destroyed there without adding much benefit to organic decomposition. A two-chamber electrolytic cell, connected with an electrolyte bridge, was developed in this work. In this new reactor, direct oxidation at anode and indirect oxidation by hydrogen peroxide at cathode can occur simultaneously. Therefore "dual electrodes oxidation" in one electrochemical reactor was achieved successfully. Compared to a traditional one cell reactor, this reactor cuts the energy cost by 50%, and thus might lead to reconsideration of the electrochemical role in wastewater treatment. A Pt/C gas diffusion electrode (GDE) is fabricated and used as a cathode fed with oxygen-containing gases to produce hydrogen peroxide. When purified air diffuses through the active layer on the GDE, oxygen is reduced to hydrogen peroxide with a high yield to decompose organics. It has been found that the direct oxidation process at an anodic zone is slightly affected by factors such as pH variation, Fe(II) existence and aeration, while indirect oxidation at the cathodic zone is strongly affected. Dye used as a model pollutant was oxidized into small organic acids in both anode and cathode regions in this electrolytic reactor. GC-MS and IR spectrum were employed to analyze the intermediates formed during the degradation. Twenty intermediates have been detected, including 14 esters, 3 acids and 3 compounds with NO2 or N-OH groups. Thereafter, the degradation pathways of dye Acid Red B are proposed.     

Removal of the pesticide methamidophos from aqueous solutions by electrooxidation using Pb/PbO2, Ti/SnO2, and Si/BDD electrodes

The anodic oxidation of methamidophos (MMD), a highly toxic pesticide used worldwide, was studied in a sodium sulfate aqueous solution on Pb/PbO2, Ti/SnO2, and Si/BDD (boron doped diamond) electrodes at 30 degrees C. Under galvanostatic conditions, it was observed thatthe performance of the electrode material is influenced by pH and current density as shown by HPLC and ATR-FTIR analysis of MMD and its oxidation products along the electrolysis. It was found that MMD degradation using Pb/PbO2 in acid media (pH 2.0 and 5.6) generates formaldehyde asthe main product of the reaction giving evidence of an indirect mineralization mechanism. Under the same conditions, Ti/SnO2 showed poor formaldehyde production compared to the Pb/PbO2 electrode. On Si/BDD electrodes formaldehyde production was not observed, instead the ATR-FTIR results showed the formation of phosphate as the reaction progressed suggesting a complete MMD mineralization on this electrode. In addition, HPLC results showed that the electrode efficiency is also dependent on the applied current density. This current density influence is remarkably clear on the Si/BDD electrodes where it was evident that the most efficient current density toward a complete MMD mineralization was reached with the application of 50 mA/cm2.     

Photo-fenton degradation of diclofenac: identification of main intermediates and degradation pathway

In recent years, the presence of pharmaceuticals in the aquatic environment has been of growing interest. These new contaminants are important because many of them are not degraded under the typical biological treatments applied in the wastewater treatment plants and represent a continuous input into the environment. Thus, compounds such as diclofenac are present in surface waters in all Europe and a crucial need for more enhanced technologies that can reduce its presence in the environment has become evident. In this sense, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous nonbiodegradable pollutants. This work deals with the solar photodegradation of diclofenac, an antiinflammatory drug, in aqueous solutions by photo-Fenton reaction. A pilot-scale facility using a compound parabolic collector (CPC) reactor was used for this study. Results obtained show rapid and complete oxidation of diclofenac after 60 min, and total mineralization (disappearance of dissolved organic carbon, DOC) after 100 min of exposure to sunlight. Although diclofenac precipitates during the process at low pH, its degradation takes place in the homogeneous phase governed by a precipitation-redissolution-degradation process. Establishment of the reaction pathway was made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Gas chromatography-mass spectrometry (GC/ MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) were used to identify 18 intermediates, in two tentative degradation routes. The main one was based on the initial hydroxylation of the phenylacetic acid moiety in the C-4 position and subsequent formation of a quinone imine derivative that was the starting point for further multistep degradation involving hydroxylation, decarboxylation, and oxidation reactions. An alternative route was based on the transient preservation of the biphenyl amino moiety that underwent a similar oxidative process of C-N bond cleavage. The proposed degradation route differs from those previously reported involving alternative degradation processes (ozonization, UV/H2O2, or photolysis), indicating that diclofenac degradation follows different pathways, depending on the treatment applied.     

热镀锌钢丝表面处理工艺

针对国内钢丝热镀锌生产能耗高、环境条件差等问题,结合现有生产实际情况,改进热镀锌钢丝表面处理生产工艺。预处理采用电解脱脂、电解酸洗、直线溢流漂洗工艺。对电解脱脂、电解酸洗机制进行分析,当温度为60～70℃,电流密度为5～15A/dm2,时间为5～10s时,脱脂效果较好;当阳极电流密度为2.0～2.5A/dm2,阴极电流密度为5.0～10.0A/dm2,时间为1～1.5min时,电解酸洗效果较好。介绍一种具有专利技术的复合助镀剂,其使用温度较常规助镀剂低15～20℃。     

活性艳蓝B-RV的电化学无盐染色

探讨了活性艳蓝B-RV的电化学无盐染色工艺,分析了电极材料、外加电压、通电时间、初染温度等因素对染色效果的影响。试验结果表明,活性艳蓝B-RV上染棉织物的最佳染色工艺条件为:外加电压5 V(阳极为银-氯化银电极,阴极为铂电极),初染温度为60℃,上染阶段通电时间25 min,固色阶段通电时间35 min。活性艳蓝在电化学条件下无盐染色比传统染色织物的K/S值高,其匀染性、染色牢度与传统染色基本一致。     

Photocatalytic degradation of acid blue 80 in aqueous solutions containing TiO2 suspensions

The photocatalytic degradation of the anthraquinonic dye Acid Blue 80 in aqueous solutions containing TiO2 dispersions has been investigated. The process has been monitored by following either the disappearance of the dye (via HPLC) and the formation of its end-products (via IC, GC, and TOC analysis). Although a relatively fast decolorization of the solutions has been observed, the mineralization is slower, and the presence of residual organic compounds was evidenced even after long term irradiation, confirming the relevant stability of anthraquinone derivatives. The identification of various unstable intermediates formed after low irradiation times was performed by HPLC-MS, allowing us to give insight into the early steps of the degradation process which mainly involve C-N bonds breaking and substrate hydroxylation. Complete and relatively fast mineralization of the substrate was achieved by irradiating the semiconductor dispersions in the presence of added K2S2O8.     

Electrolyte management for effective long-term electro-osmotic transport in low-permeability soils

Electro-osmosis, a coupled-flow phenomenon in which an applied electrical potential gradient drives water flow, may be used to induce water flow through fine-grained sediments. Test cell measurements of electro-osmotic transport in clayey cores extracted from the 27-31 m depth range of the Lawrence Livermore National Laboratory site indicate the importance of pH control within the anode and cathode reservoirs. In our first experiment, pH was not controlled. As a result, carbonate precipitation and metals precipitation occurred near the cathode end of the core, with acidification near the anode. The combination of these acid and base reactions led to the decline of electro-osmotic flow by a factor of 2 in less than one pore volume. In a second experiment, long-term water transport (>21 pore volumes) at stable electro-osmotic conductivity (k(eo) approximately 1 x 10(-9) m2/s-V) was effected with anode reservoir pH > 8, and cathode reservoir pH < 6. Hydraulic conductivity (k(h)) of the same core was 4 x 10(-10) m/s under a 0.07 MPa hydraulic gradient without electro-osmosis. Stable electro-osmotic flow was measured at a velocity of 4 x 10(-7) m/s under a 4 V/cm voltage gradient, and no hydraulic gradient-3 orders of magnitude greater than the hydraulic flow. We also observed chloroform production in the anode reservoir, resulting from electrochemical production of chlorine gas reacting with trace organics. The chloroform was transported electro-osmotically to the cathode, without measurable loss to adsorption, volatilization, or degradation.     

纳米ZnO对聚丙烯薄膜中抗氧化剂168降解的影响

利用气相色谱-质谱研究在日照、紫外、微波处理条件下,纳米ZnO/聚丙烯复合膜中纳米ZnO对抗氧化剂168降解的影响。结果表明,日照、紫外处理纳米ZnO/聚丙烯复合膜,抗氧化剂168的降解会随着处理时间的延长而增加,直至达到平衡。在日照12?d之后,复合膜中的纳米ZnO对抗氧化剂168的降解开始有促进作用,且日照处理下偶联剂的加入对抗氧化剂168的降解有一定影响。与日照处理相比,紫外处理使得抗氧化剂168降解更为剧烈,其中一种降解产物——2,4-二叔丁基苯酚的含量随紫外照射时间的延长呈现先上升（紫外照射24?h达到最高点）后下降的趋势,紫外照射13?h之后,复合膜中的纳米ZnO对抗氧化剂168的降解开始有抑制作用,且紫外处理下偶联剂的加入对抗氧化剂168的降解影响不大,仅对另一种降解产物——三（2,4-二-叔丁基苯基）磷酸酯的生成有一定影响。微波功率的增加能促进抗氧化剂168的降解,但微波次数的增加和纳米ZnO及偶联剂的加入对抗氧化剂168的降解无显著影响。     

Redox control for electrochemical dechlorination of trichloroethylene in bicarbonate aqueous media

The role of iron anode on electrochemical dechlorination of aqueous trichloroethylene (TCE) is evaluated using batch mixed-electrolyte experiments. A significantly higher dechlorination rate, up to 99%, is reported when iron anode and copper foam cathodes are used. In contrast to the oxygen-releasing inert anode, the cast iron anode generates ferrous species, which regulate the electrolyte to a reducing condition (low ORP value) and favor the reduction of TCE. The main products of TCE electrochemical reduction on copper foam cathode include ethene and ethane. The ratio of these two hydrocarbons gases varied with the electrolyte ORP condition and current density as more ethane gas generates at more reducing electrolyte condition and at higher current condition. A pseudofirst-order model is used to describe the degradation of TCE; the first-order rate constant (k) increases with the current applied but exhibits a negative relation with initial concentration. Depending on the current, electrolysis by iron anode causes a reduction in the ORP and an increase in the pH of the mixed electrolyte. Enhanced reaction rates in this investigation indicate that the electrochemical reduction using copper foam and iron anode may be a promising process for remediation of groundwater contaminated with chlorinated organic compounds.     

电解法制备超细铜粉的工艺研究

采用脉冲电解法,在硫酸铜与硫酸混合电解溶液体系中,就不同脉冲电解参数对阴极铜粉形貌和粒度的影响进行了研究.实验获得合适的脉冲参数为平均电流密度i=600 A/m2,脉冲宽度ton=8ms,占空比为1∶3,在此条件下,所得铜粉平均粒度为0.87μm,有90%颗粒粒径小于1.25μm,阴极沉积出的铜粉颗粒粒度在0.24~1.79μm之间,粒度分布均匀.     

Destruction of gas-phase trichloroethylene in a modified fuel cell

A conventional fuel cell was used as a catalytic reactor to treat soil vapor extraction (SVE) gases contaminated with trichloroethylene (TCE). The SVE gases are fed to the cathode side of the fuel cell, where TCE is reduced to ethane and hydrochloric acid. The results obtained suggest that TCE reduction occurs by a catalytic reaction with hydrogen that is re-formed on the cathode's surface beyond a certain applied cell potential. Substantial conversion of TCE is obtained, even when competing oxygen reduction occurs in the cathode. The process has been modeled successfully by conceptualizing the flow passage in the fuel cell as a plug flow reactor.     

Production of electricity during wastewater treatment using a single chamber microbial fuel cell

Microbial fuel cells (MFCs) have been used to produce electricity from different compounds, including acetate, lactate, and glucose. We demonstrate here that it is also possible to produce electricity in a MFC from domestic wastewater, while atthe same time accomplishing biological wastewater treatment (removal of chemical oxygen demand; COD). Tests were conducted using a single chamber microbial fuel cell (SCMFC) containing eight graphite electrodes (anodes) and a single air cathode. The system was operated under continuous flow conditions with primary clarifier effluent obtained from a local wastewater treatment plant. The prototype SCMFC reactor generated electrical power (maximum of 26 mW m(-2)) while removing up to 80% of the COD of the wastewater. Power output was proportional to the hydraulic retention time over a range of 3-33 h and to the influent wastewater strength over a range of 50-220 mg/L of COD. Current generation was controlled primarily by the efficiency of the cathode. Optimal cathode performance was obtained by allowing passive air flow rather than forced air flow (4.5-5.5 L/min). The Coulombic efficiency of the system, based on COD removal and current generation, was < 12% indicating a substantial fraction of the organic matter was lost without current generation. Bioreactors based on power generation in MFCs may represent a completely new approach to wastewater treatment. If power generation in these systems can be increased, MFC technology may provide a new method to offset wastewater treatment plant operating costs, making advanced wastewater treatment more affordable for both developing and industrialized nations.     

Degradation of herbicide 4-chlorophenoxyacetic acid by advanced electrochemical oxidation methods

The herbicide 4-chlorophenoxyacetic acid (4-CPA) has been degraded in aqueous medium by advanced electrochemical oxidation processes such as electro-Fenton and photoelectro-Fenton with UV light, using an undivided cell containing a Pt anode. In these environmentally clean methods, the main oxidant is the hydroxyl radical produced from Fenton's reaction between Fe2+ added to the medium and H2O2 electrogenerated from an 02-diffusion cathode. Solutions of a 4-CPA concentration <400 ppm within the pH range of 2.0-6.0 at 35 degrees C can be completely mineralized at low current by photoelectro-Fenton, while electro-Fenton leads to ca. 80% of mineralization. 4-CPA is much more slowly degraded by anodic oxidation in the absence and presence of electrogenerated H2O2. 4-Chlorophenol, 4-chlorocatechol, and hydroquinone are identified as aromatic intermediates by CG-MS and quantified by reverse-phase chromatography. Further oxidation of these chloroderivatives yields stable chloride ions. Generated carboxylic acids such as glycolic, glyoxylic, formic, malic, maleic, fumaric, and oxalic are followed by ion exclusion chromatography. The highest mineralization rate found for photoelectro-Fenton is accounted for by the fast photodecomposition of complexes of Fe3+ with such short-chain acids, mainly oxalic acid, under the action of UV light.     

西红花苷-1的稳定性研究

采用化学动力学方法研究pH值、温度、光照、初始质量浓度对西红花苷-1稳定性的影响。结果表明:西红花苷-1在溶液中的降解反应为表观一级反应,pH值、温度、光照、初始质量浓度均能够影响其稳定性,在pH6.0～7.0之间时最稳定,在自然光照射下的反应速率较紫外光更快,对温度极其敏感,但反应速率常数与其初始反应质量浓度无关,其在溶液中降解反应活化能Ea为45.36kJ/mol。     

磁载纳米TiO_2复合粉体处理印染废水

以纳米SiO2/Fe3O4为载体,采用溶胶-凝胶法制备了ZnO掺杂的磁载纳米TiO2复合粉体,并对印染废水进行太阳光催化降解处理。通过透射电子显微镜等进行表征,并测定了其对印染废水的光催化降解性能。结果表明,当复合粉体用量为1g/L,印染废水pH值为8,复合粉体中ZnO与TiO2的质量分数比为3%,载体SiO2/Fe3O4用量为22%时,经太阳光照射6h后,脱色率达到68.7%,并能有效实现粉体与废水的分离及回收利用。     

TiO2-based photocatalytic degradation of 2-chlorophenol adsorbed on hydrophobic clay

The combination of adsorption and heterogeneous photocatalysis has been investigated as a promising technology for the removal of organic water pollutants. A laboratory study of the removal and decomposition of 2-chlorophenol (2-CP) as a toxic organic pollutant was carried out under various conditions with an organophilized clay mineral (hexadecylpyridinium chloride-modified montmorillonite; HDPM) as adsorbent and Degussa P25 TiO2 as photocatalyst. Three different oxidation processes leading to the degradation of 2-CP were compared: direct photolysis, heterogeneous photocatalysis in a TiO2 suspension, and the decomposition of substrate adsorbed on HDPM in the presence of TiO2. Both the degradation of 2-CP and the formation of intermediates were analyzed by HPLC, the total organic carbon content and the total organic and inorganic chloride contents were measured to monitor the mineralization process, and X-ray diffraction and thermoanalytical measurements were made to characterize the hydrophobic clay adsorbent. The heterogeneous photocatalytic degradation of dissolved (2-CP/UV/TiO2) and desorbed 2-CP (2-CP/HDPM/UV/TiO2) appeared to be equally efficient, whereas direct photolysis of 2-CP was far less efficient in the oxidative destruction. HDPM proved to be a suitable adsorbent, capable of adsorbing toxic organics from water. It was demonstrated that the adsorbent (at relatively high concentration) did not decrease the rate of mineralization of 2-CP. The results confirmed that the adsorbent retains its structure and composition during the mineralization process, and thus it can be reused without regeneration. The combination of adsorption and heterogeneous photocatalysis studied may be an efficient and economical means of accumulating, removing, and oxidizing organic water contaminants, and its application is in accordance with the growing environmental demands.