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1.
Hydrogen production with a microbial biocathode   总被引:11,自引:0,他引:11  
This paper, for the first time, describes the development of a microbial biocathode for hydrogen production that is based on a naturally selected mixed culture of electrochemically active micro-organisms. This is achieved through a three-phase biocathode startup procedure that effectively turned an acetate- and hydrogen-oxidizing bioanode into a hydrogen-producing biocathode by reversing the polarity of the electrode. The microbial biocathode that was obtained in this way had a current density of about -1.2 A/Nm2 at a potential of -0.7 V. This was 3.6 times higher than that of a control electrode (-0.3 A/m2). Furthermore, the microbial biocathode produced about 0.63 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 49% during hydrogen yield tests, whereas the control electrode produced 0.08 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 25%. The effluent of the biocathode chamber could be used to inoculate another electrochemical cell that subsequently also developed an identical hydrogen-producing biocathode (-1.1 A/m2 at a potential of -0.7 V). Scanning electron micrographs of both microbial biocathodes showed a well-developed biofilm on the electrode surface.  相似文献   

2.
Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zerovalent, which shows the difficulty with in-situ synthesis of a significant fraction of zerovalent iron in the microporous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogeneous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI.  相似文献   

3.
Polychlorinated biphenyls (PCBs) are toxic pollutants notorious for their aquatic and sedimentary prevalence and recalcitrant nature. Bimetallic systems like Pd/Fe have been widely studied for degrading them. Mg, with oxidation potential higher than Fe, has been reported to dechlorinate PCBs in conjunction with K2PdCl6-systems that are distinct from Pd/Mg bimetals. This study primarily aims to evaluate Pd/Mg bimetallic systems for dechlorinating 2-chlorobiphenyl (2-CIBP), a model PCB. Candidacy of Mg is based on its unique corrosion properties that afford synthesis and storage under ambient conditions and application-based advantages. A simple wet-chemistry procedure was developed to synthesize Pd/Mg particles with 0.11-1.62% Pd content and nanoscale Pd-islands as determined by X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM). Aqueous 2-CIBP matrices were effectively degraded using these particles, the dechlorination kinetics showing linear dependence on the total Pd content. The pH profile obtained with varying bimetallic content led to useful insights into the unique behavior of Mg surface. A carbon mole balance showed 85-105% recoveries. Performance of the Pd/Mg particles in PCB spiked clays and sediment suggests that they may work well in such systems. Finally, a mechanism for PCB dechlorination in Pd/Mg systems was proposed.  相似文献   

4.
In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.  相似文献   

5.
There is a need for alternative catalysts for oxygen reduction in the cathodic compartment of a microbial fuel cell (MFC). In this study, we show that a bipolar membrane combined with ferric iron reduction on a graphite electrode is an efficient cathode system in MFCs. A flat plate MFC with graphite felt electrodes, a volume of 1.2 L and a projected surface area of 290 cm2 was operated in continuous mode. Ferric iron was reduced to ferrous iron in the cathodic compartment according to Fe(3+) + e(-) --> Fe2+ (E0 = +0.77 V vs NHE, normal hydrogen electrode). This reversible electron transfer reaction considerably reduced the cathode overpotential. The low catholyte pH required to keep ferric iron soluble was maintained by using a bipolar membrane instead of the commonly used cation exchange membrane. For the MFC with cathodic ferric iron reduction, the maximum power density was 0.86 W/m2 at a current density of 4.5 A/m2. The Coulombic efficiency and energy recovery were 80-95% and 18-29% respectively.  相似文献   

6.
研究了多壁纳米碳管(MWNTs)在碱性电解液中的电化学行为.结果表明:电极集流体结构对其电化学活性有较大影响;循环伏安曲线显示,氢在MWNTs上的电化学反应可逆性随循环次数增加而有一定改善;阴极极化曲线表明了MWNTs不同类型上的氢析出电位有一定差别.认为MWNTs在碱性电解液中氢的电化学反应可逆,氢析出电位与MWNTs类型有关.  相似文献   

7.
研制金钯合金纳米粒子修饰的特异性定量检测食品中过氧化氢残留量的过氧化氢传感器。以比表面积大、生物相容性好、具有优良电催化性能的金钯合金纳米粒子固定辣根过氧化物酶于玻碳电极,制得过氧化氢传感器电极。通过循环伏安法及交流阻抗法表征电极在组装过程中的电化学特性,利用计时电流法对传感器性能进行考察。研究表明:该传感器测定H2O2的线性范围为1×10-7~5×10-3mol/L,检测限为8.0×10-7 mol/L,对H2O2具有较好的催化还原活性和良好的检出性能。该传感器制作简单、成本低廉、可重复性强,可用于快速定量检测食品中过氧化氢残留量。  相似文献   

8.
The combination of zerovalent metal with a catalytic second metal ion (bimetallic materials) to enhance the dechlorination efficiency and rate of chlorinated compounds has received much attention. Bimetallic materials not only enhance the dechlorination process but also alter the reduction pathway and product distribution. In this study, the efficiency and rate of tetrachloroethylene (PCE) dechlorination by metal-modified zerovalent silicon was investigated as a potential reductant for chlorinated hydrocarbons under anoxic conditions. The X-ray photoelectron spectroscopic (XPS) results showed that metal ions including Ni(II), Cu(II), and Fe(II) could be reduced to their zerovalent forms on the Si surface. The dechlorination of PCE obeyed the pseudo-first-order kinetics, and the pseudo-first-order rate constants (k(obs)) for PCE dechlorination followed the order Ni/Si > Fe/Si > Cu/Si. Addition of Cu(II) lowered the dechlorination efficiency and rate of PCE by Si, while the k(obs) values for PCE dechlorination in the presence of 0.1 mM Fe(II) and Ni(II) were 1.5-3.8 times higher than that by Si alone. In addition, the efficiency and rate of PCE dechlorination increased upon increasing the mass loading of Ni(II) ranging between 0.05 and 0.5 mM and then decreased when the Ni(II) loading was further increased to 1 mM. The scanning electron microscopic (SEM) images and electron probe microanalytical (EPMA) maps showed that the Ni nanoparticles deposited on the Si surface and aggregated to a large particle at 1 mM Ni(II), which clearly depicts that the Ni(II) loading of 0.5 mM is the optimal value to enhance the efficiency and rate of PCE dechlorination by Si. Also, the reaction pathways for PCE dechlorination changed from hydrogenolysis in the absence of Ni(II) to hydrodechlorination when Ni(II) concentrations were higher than 0.05 mM. Results obtained in this study reveal that the metal-deposited zerovalent silicon can serve as an environmentally friendly reductant for the enhanced degradation of chlorinated hydrocarbons for long-term performance.  相似文献   

9.
The combined removal of chlorinated ethenes and heavy metals from a simulated groundwater matrix by zerovalent iron (ZVI) was investigated. In batch, Ni (5-100 mg L(-1)) enhanced trichloroethene (TCE, 10 mg L(-1)) reduction by ZVI (100 g L(-1)) due to catalytic hydrodechlorination by bimetallic Fe0/Ni0. Cr(VI) or Zn (5-100 mg L(-1)) lowered TCE degradation rates by a factor of 2 to 13. Cr(VI) (100 mg L(-1)) in combination with Zn or Ni (50-100 mg L(-1)) inhibited TCE degradation. Addition of 20% H2(g) in the headspace, or of Zn (50-100 mg L(-1)), enhanced TCE removal in the presence of Ni and Cr(VI). Sorption of Zn to ZVI alleviated the Cr(VI) induced inhibition of bimetallic Fe0/Ni0 apparently due to release of protons necessary for TCE hydrodechlorination. In continuous ZVI columns treating tetrachloroethene (PCE, 1-2 mg L(-1)) and TCE (10 mg L(-1)), and a mixture of the metals Cr(VI), Zn(II), and Ni(II) (5 mg (L-1)), the PCE removal efficiency decreased from 100% to 90% in columns operated without heavy metals. The PCE degradation efficiency remained above 99% in columns receiving heavy metals as long as Ni was present. The findings of this study indicate the feasibility and limitations of the combined treatment of mixtures of organic and inorganic pollutants by ZVI.  相似文献   

10.
Nitration of benzo[a]pyrene (BaP) by nitrogen dioxide (NO2) adsorbed on the surface of thermally activated coal fly ash and model aluminosilicate particles led to the formation of nitrobenzo[a]pyrenes as verified by extraction and gas chromatography/mass spectrometry (GC/MS). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was utilized to follow the nitration reaction on the surface of zeolite Y. Nitrobenzo[a]pyrene formation was observed along with the formation of nitrous acid and nitrate species. The formation of the BaP radical cation was also observed on thermally activated aluminosilicate particles by electron spin resonance (ESR) spectroscopy. On the basis of GC/MS, DRIFTS, and ESR spectroscopy results, a mechanism of nitration involving intermediate BaP radical cations generated on thermally activated aluminosilicate particles is proposed. These observations have led to the hypothesis that nitration of adsorbed polyaromatic hydrocarbons on coal fly ash by reaction with nitrogen oxides can occur in the smokestack, but with the aging of the fly ash particles, the extent of the nitration reaction will be diminished.  相似文献   

11.
A Ni catalyst was added to a cis-selective Pd catalyst in an attempt to further improve the Pd catalyst's cis-selectivity and activity for canola oil hydrogenation. The system was tested under reaction conditions known to be suitable for cis-selective hydrogenation with the Pd catalyst (50 ppm Pd, 70 °C, and 5.2 MPa). Although inactive on its own under these conditions, the addition of 100 ppm Ni increased the hydrogenation activity (from 2.12 to 2.49 10−2 min−1). Further addition of Ni up to 1000 ppm resulted in no further improvements in activity. The trans isomer contents of the oils hydrogenated with Pd and the Pd/Ni systems were similar. The level of conjugated dienes decreased rapidly during hydrogenation with both Pd alone and with the Pd/Ni combination and no changes in conjugation were detected in the presence of the Ni catalyst alone. The increased activity of the Pd/Ni system over Pd alone was attributed to adsorption of catalyst poisons from the oil by Ni.  相似文献   

12.
Nanoscale Fe0 particles are a promising technology for in situ remediation of trichloroethene (TCE) plumes and TCE-DNAPL source areas, butthe physical and chemical properties controlling their reactivity are not yet understood. Here, the TCE reaction rates, pathways, and efficiency of two nanoscale Fe0 particles are measured in batch reactors: particles synthesized from sodium borohydride reduction of ferrous iron (Fe/B) and commercially available particles (RNIP). Reactivity was determined under iron-limited (high [TCE]) and excess iron (low [TCE]) conditions and with and without added H2. Particle efficiency, defined as the fraction of the Fe0 in the particles that is used to dechlorinate TCE, was determined under iron-limited conditions. Both particles had a core/shell structure and similar specific surface areas (approximately 30 m2/g). Using excess iron, Fe/B transformed TCE into ethane (80%) and C3-C6 coupling products (20%). The measured surface area normalized pseudo-first-order rate constant for Fe/B (1.4 x 10(-)2 L.h(-1).m(-2) is approximately 4-fold higher than for RNIP (3.1 x 10-(3) L.h(-1).m(-2). All the Fe0 in Fe/B was accessible for TCE dechlorination, and 92 +/- 0.7% of the Fe0 was used to reduce TCE. For Fe/B, H2 evolved from reduction of water (H+) was subsequently used for TCE dechlorination, and adding H2 to the reactor increased both the dechlorination rate and the mass of TCE reduced, indicating that a catalytic pathway exists. RNIP yielded unsaturated products (acetylene and ethene). Nearly half (46%) of the Fe0 in RNIP was unavailable for TCE dechlorination over the course of the experiment and remained in the particles. Adding H2 did not change the reaction rate or efficiency of RNIP. Despite this, the mass of TCE dechlorinated per mass of Fe0 added was similar for both particles due to the less saturated products formed from RNIP. The oxide shell composition and the boron content are the most likely causes for the differences between the particle types.  相似文献   

13.
Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was accomplished through the addition of iron (Fe) and hydrogen peroxide (H2O2) (15.9 g/L; pH 3). The Fe concentration in GAC was incrementally varied (1020-25 660 mg/kg) by the addition of increasing concentrations of Fe solution (FeSO4-7H2O). MTBE degradation in Fe-amended GAC increased by an order of magnitude over Fe-unamended GAC and H2O2 reaction was predominantly (99%) attributed to GAC-bound Fe within the porous structure of the GAC. Imaging and microanalysis of GAC particles indicated limited penetration of Fe into GAC. The optimal Fe concentration was 6710 mg/kg (1020 mg/kg background; 5690 mg/kg amended Fe) and resulted in the greatest MTBE removal and maximum Fe loading oxidation efficiency (MTBE oxidized (microg)/ Fe loaded to GAC (mg/Kg)). At lower Fe concentrations, the H2O2 reaction was Fe limited. At higher Fe concentrations, the H2O2 reaction was not entirely Fe limited, and reductions in GAC surface area, GAC pore volume, MTBE adsorption, and Fe loading oxidation efficiency were measured. Results are consistent with nonuniform distribution of Fe, pore blockage in H2O2 transport, unavailable Fe, and limitations in H2O2 diffusive transport, and emphasize the importance of optimal Fe loading.  相似文献   

14.
Effect of cathodic enzymatic decolorization of reactive blue 221 (RB221) on the performance of a dual-chamber microbial fuel cell (MFC) was investigated. Immobilized laccase on the surface of a modified graphite electrode was used in the cathode compartment in order to decolorize the azo dye and enhance the oxygen reduction reaction. First, methylene blue which is an electroactive polymer was electropolymerized on the surface of a graphite bar to prepare the modified electrode. Utilization of the modified electrode with no enzyme in the MFC increased the power density up to 57% due to the reduction of internal resistance from 1000 to 750 Ω. Using the electropolymerized-enzymatic cathode resulted in 65% improvement of the power density and a decolorization efficiency of 74%. Laccase could act as a biocatalyst for oxygen reduction reaction along with catalyzing RB221 decolorization. Treatment of RB221 with immobilized laccase reduced its toxicity up to 5.2%. Degradation products of RB221 were identified using GC-MS, and the decomposition pathway was proposed. A discussion was also provided as to the mechanism of dye decolorization on the enhancement of the MFC performance.  相似文献   

15.
Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing ?OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% ?OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and ?OH generation rate constants confirms that ?OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.  相似文献   

16.
Bimetallic reductants are frequently more reactive toward organohalides than unamended iron and can also alter product distributions, yet a molecular-level explanation for these phenomena remains elusive. In this study, surface characterization of six iron-based bimetallic reductants (Au/Fe, Co/Fe, Cu/Fe, Ni/Fe, Pd/Fe, and Pt/Fe) revealed that displacement plating produced a non-uniform overlayer of metallic additive on iron. Batch studies demonstrated that not all additives enhanced rates of 1,1,1-trichloroethane (1,1,1-TCA) reduction nor was there any clear periodic trend in the observed reactivity (Ni/Fe approximately Pd/Fe > Cu/Fe > Co/ Fe > Au/Fe approximately Fe > Pt/Fe). Pseudo-first-order rate constants for 1,1,1-TCA reduction (kobs values) did, however, correlate closely with the solubility of atomic hydrogen within each additive. This suggests absorbed atomic hydrogen, rather than galvanic corrosion, is responsible for the enhanced reactivity of bimetallic reductants. In addition, all additives shifted product distributions to favor the combined yield of ethylene plus ethane over 1,1-dichloroethane. In rate-enhancing bimetallic systems, branching ratios between 1,1-dichloroethane and the combination of ethylene and ethane were uniquely dependent on kobs values, indicating an intimate link between rate-determining and product-determining steps. We propose that our results are best explained by an X-philic pathway involving atomic hydrogen with a hydride-like character.  相似文献   

17.
Monochlorobenzene (MCB), dichlorobenzenes (DCBs), and 1,2,4-trichlorobenzene (124TCB) dechlorination experiments in water were carried out with freshly synthesized Pd/Fe particles. The pre- and postreacted Pd/Fe samples were characterized by applying various analytical techniques (XRD, SEM, TEM, and XPS). Chlorinated benzenes could be completely reduced by the Pd/Fe to benzene and the reaction followed the pseudo-first-order kinetics. The reaction rates followed the order TCB < DCBs < MCB, while among the DCBs the order was 1,4-dichlorobenzene >1,3-dichlorobenzene > or = 1,2-dichlorobenzene. Insignificant reactions were observed with the unpalladized iron, suggesting that Pd was the only reactive site in the Pd/Fe particles. The aged Pd/Fe particles exhibited significant decrease in its dechlorination reactivity. The loss of Pd/Fe reactivity could be due to Pd dislodgment from the aged Pd/Fe particles and Pd islets encapsulation by the iron oxides film developed over aging period. Reactivity of the aged Pd/Fe could be only partially restored after HCI treatment, while regeneration with the NaBH4 reduction method could not restore its activity, although zerovalent state of the iron was reinstated.  相似文献   

18.
Alumina-supported palladium (Pd) catalysts have previously been shown to hydrodechlorinate trichloroethene (TCE) and other chlorinated compounds in water, at room temperature, and in the presence of hydrogen. The feasibility of this catalytic technology to remediate groundwater of halogenated compounds can be improved by re-designing the Pd material in order to increase catalytic activity. We synthesized and characterized Pd supported on gold nanoparticles (Au NPs) of different Pd loadings. In all cases, we found that these catalysts were considerably more active than Pd NPs, alumina-supported Pd, ard Pd-black (62.0, 12.2, and 0.42 L x g(Pd)(-1) x min(-1), respectively). There is a synergistic effect of the Pd-on-Au bimetallic structure, with the material with the highest TCE hydrodechlorination activity (943 L x g(Pd)(-1) x min(-1)) comprised of Au NPs partially covered by Pd metal. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. The resulting nanoparticle-based materials should be highly suitable as hydrodehalogenation and reduction catalysts for the remediation of various organic and inorganic groundwater contaminants.  相似文献   

19.
Pd/C催化下麦草碱木质素与氢气的还原反应   总被引:3,自引:0,他引:3  
以钯/炭(Pd/C)为催化剂,以氢气为还原剂与麦草碱木质素进行反应,分析了不同反应条件对催化效果的影响,用化学法测定了反应前后碱木质素官能团的含量,并与环己烯还原法进行了比较。结果表明,在Pd/C催化剂负载量为3%、用量0.1g/g、氢气流速20mL/min、反应温度363K、反应时间3h的条件下,反应后碱木质素的总羟基、酚羟基、醇羟基含量分别为14.39%、4.21%和10.18%,较反应前分别增加了133.68%、27.96%和264.87%。与环己烯法相比,氢气还原法的催化剂用量明显减少,醇羟基数增加较为显著,酚羟基含量基本一致。氢气还原活化效果明显优于环己烯还原效果。  相似文献   

20.
采用置换镀镍工艺对贮氢合金粉进行了表面包覆处理.交流阻抗、循环伏安及模拟电池充放电实验表明,经过置换镀镍处理后,降低了贮氢合金电极表面的电化学反应阻抗,提高了电化学反应活性,明显改善了贮氢合金电极的充放电性能及活化性能.  相似文献   

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