Catalytic dechlorination of monochlorobenzene with a new type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant

A unique type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant was prepared and used for dechlorination of monochlorobenzene (MCB). The sample Ni(B)/Fe(B) was synthesized by an electroless plating method, in which nanoscale Ni(B) was deposited on the surface of nanoscale Fe(B) synthesized by chemical reduction. The results suggest that the nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant has higher dechlorination efficiency than Ni/Fe(B) catalytic reductant prepared by replacing Fe(B) with Ni(2+) in aqueous solution. The Ni content was found to be an important factor in catalytic dechlorination, with the dechlorination rate increasing with Ni content. The electroless plating method improve the efficiency of the Ni(2+) in the solution. Dechlorination takes place with the existence of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant via a pseudo-first-order reaction.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用,给人类带来了较大危害.为此,采用纳米铁粉这一新方法对其进行脱氯处理.试验以纳米级铁粉对四氯化碳的脱氯率为考察指标,选用L25(56)正交试验方案,考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素.结果表明,pH值这一因素有极显著影响;在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下,获得了99.5%的脱氯率,为有机氯化物脱氯开辟了一条新途径.     

Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions

In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol⁻¹, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.     

Dechlorination of hexachlorobenzene using lead–iron bimetallic particles

Synthesized lead–iron (Pb/Fe) bimetallic particles were applied to dechlorinate hexachlorobenzene (HCB) under various conditions (e.g. bimetal amount, initial pH value, reaction temperature, and reaction duration). The results showed that adding Pb onto Fe benefited the dechlorination of HCB and the bimetal with 1.4% Pb content performed best. The degradation rate decreased regularly as the initial pH value of the aqueous increased from 1.9 to 11.1 except for pH 7.0 where the fastest dechlorination rate emerged. The dechlorination could be enhanced by increasing the amount of Pb/Fe or the reaction temperature. The dechlorination ratio of HCB within 15 min increased from 24.3% to 81.3% when Pb/Fe amount increased from 0.1 g to 0.8 g. The dechlorination followed pseudo-first-order kinetics, and the dechlorination rate constants were 0.0027, 0.0064, 0.0157, and 0.0321 min^?1 at 25, 50, 70, and 85 °C, respectively, and the activation energy (E_a) of the dechlorination by Pb/Fe was 37.86 kJ mol^?1.     

Catalytic dechlorination kinetics of p-dichlorobenzene over Pd/Fe catalysts

p-Dichlorobenzene (p-DCB) was dechlorinated using Pd/Fe bimetallic catalytic reductants synthesized by chemical deposition. Batch experiments demonstrated that the Pd/Fe bimetallic particles could effectively dechlorinate p-DCB, p-DCB and its intermediate chlorobenzene were removed completely at a Pd loading of 0.02% (weight ratio of Pd to Fe) and Pd/Fe power to solution ratio about 4g 75 ml-1 in 90 min. Dechlorination was affected by various factors such as the reaction temperature, pH, Pd loading percentage over Fe and the introduction of Pd/Fe catalysts et al. Chlorobenzene represents partially stable dechlorinated intermediates in the generation of benzene and part of p-DCB was dechlorinated to benzene indirectly on the surface of Pd/Fe. The dechlorination of p-DCB took place on the surface of the Pd/Fe bimetallic particles in a pseudo-first-order reaction, the activation energy of the dechlorination reaction was determined to be 80.0 kJ mol-1 at the temperature range of 287-313 K.     

Catalytic amination and dechlorination of para-nitrochlorobenzene (p-NCB) in water over palladium-iron bimetallic catalyst

Chemical treatment of para-nitrochlorobenzene (p-NCB) by palladium/iron (Pd/Fe) bimetallic particles represents one of the latest innovative technologies for the remediation of contaminated soil and groundwater. The amination and dechlorination reaction is believed to take place predominantly on the surface site of the Pd/Fe catalysts. The p-NCB was first transformed to p-chloroaniline (p-CAN) then quickly reduced to aniline. 100% of p-NCB was removed in 30 min when bimetallic Pd/Fe particles with 0.03% Pd at the Pd/Fe mass concentration of 3g 75 ml(-1) were used. The p-NCB removal efficiency and the subsequent dechlorination rate increased with the increase of bulk loading of palladium and Pd/Fe. As expected, p-NCB removal efficiency increased with temperature as well. In particular, the removal efficiency of p-NCB was measured to be 67%, 79%, 80%, 90% and 100% for reaction temperature 20, 25, 30, 35 and 40 degrees C, respectively. Our results show that no other intermediates were generated besides Cl(-), p-CAN and aniline during the catalytic amination and dechlorination of p-NCB.     

Bimetallic iron-aluminum particles for dechlorination of carbon tetrachloride

Bimetallic iron-aluminum (Fe/Al) particles were synthesized and tested for their reactivity toward carbon tetrachloride using batch reactors and a flow-through column at near neutral pH. Preparation of bimetallic Fe/Al particles was conducted under acidic conditions under which iron was readily deposited onto the aluminum surface. The SEM image showed clusters of iron on the aluminum surface at the measured Fe:Al molar ratio of about 2:3. Results showed that the presence of zero-valent aluminum successfully prevented the formation of a passive layer at the iron surface and maintained the reactivity of iron. The dechlorination of carbon tetrachloride by bimetallic Fe/Al particles produced chloroform (9%), dichloromethane (17%) and methane (38%). Kinetic analysis suggests that bimetallic Fe/Al particles increased the reactivity toward carbon tetrachloride degradation by a factor of 10 compared to zero-valent iron and possessed a comparable reactivity with nano-sized Fe. The effectiveness of bimetallic Fe/Al particles was further confirmed by the continuous flow column study from which an ageing of bimetallic particles was also observed.     

钯/铝双金属体系对3-氯酚的脱氯降解

研究了钯/铝双金属体系对水相中3-氯酚的催化脱氯降解效果,通过置换沉积制备了钯/铝双金属颗粒,考察了该双金属颗粒的稳定性以及溶液pH和钯负载量对脱氯效果的影响。结果表明,pH在4.0以下的酸性条件,钯负载量在1.43%时,可实现水相中3-氯酚的有效脱氯,反应30 min后0.389 mmol/L的3-氯酚转化率可达99%以上,产物主要为苯酚,而钯/铝颗粒在重复测试中能保持较好的稳定性,这与铝基材表面自发形成的氧化膜有关。钯/铝材料表征的结果表明,钯颗粒高度分散在铝基材表面,并极大地提高了铝基材的表面积,从而有助于后续的脱氯反应。     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

Sonochemical degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxins in aqueous solution with Fe(III)/UV system

2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD) was rapidly decreased by sonication in aqueous solution. The degradation efficiency was strongly influenced by ultrasonic power and reaction temperature. An initial 2,3,7,8-TeCDD concentration of 20 ng l(-1) was completely degraded within 60 min under sonochemical conditions using a 20 kHz frequency with a 150 W ultrasound power. The activation energy is 21.9 kJ/mol in the temperature range of 10-40 degrees C, suggesting a diffusion-controlled reaction. To increase the efficiency of 2,3,7,8-TeCDD treatment, degradation system combined ultrasound with Fe(III) (2 x 10(-4)mol l(-1)) and UV irradiation. Both UV and Fe(III) induced Fenton, Fenton-like and photo-Fenton reactions, leading to additional OH radicals and rapid 2,3,7,8-TeCDD removal.     

A combination of electrokinetics and Pd/Fe PRB for the remediation of pentachlorophenol-contaminated soil

Electrokinetic (EK) remediation of pentachlorophenol (PCP)-contaminated soil is difficult because PCP dissociates at different pH values along soil column and shows different transport behaviors near anode and cathode. In the present study, a permeable reactive barrier (PRB) filled with reactive Pd/Fe particles was installed between anode and cathode to reach the dechlorination of PCP during its EK movement. When PRB was installed at the position of 0.3 (normalized distance from anode), PCP in the section from anode to PRB could transport through PRB, while PCP in the section from cathode to PRB was accumulated near PRB. PCP was hardly dechlorinated by PRB wherein high pH was reached. When PRB was installed at the position of 0.5 and the pH in the PRB was decreased by periodical injection of HAc, 49% of PCP was removed, and 22.9% was recovered as phenol which was mostly collected in catholyte. The mechanism of PCP removal was proposed as the EK movement of PCP into the PRB compartment, the complete dechlorination of PCP to phenol by Pd/Fe in the PRB compartment, and the subsequent removal of phenol by electroosmosis. This study proved that the combination of electrokinetics and Pd/Fe PRB was effective for the remediation of PCP-contaminated soil.     

Enhanced photocatalysis of pentachlorophenol by metal-modified titanium (IV) oxide

The effects of four metals (Ag, Au, Pt, and Cu) doped on TiO2 on the photocatalysis of pentachlorophenol (PCP) were investigated. The results of this study indicated that all four metals-doped TiO2 catalysts were able to enhance the efficiency of PCP photocatalysis with an optimum metallic content of 0.1 wt%. For the metal-doped TiO2 samples (Au, Pt, and Cu), the patterns of light absorption were significantly extended toward visible light spectra in the wavelengths between 400 and 800 nm. The photocatalysis of PCP was pH dependent with the maximum degradation rate achieved in the solution at pH 3. The formation of chloride ion corresponded with the concentration of PCP degraded which confirmed that dechlorination was the major pathway of PCP photocatalysis. The overall toxicities of PCP samples were reduced with the extension of light exposure using the microtox test. The results of PCP photocatalysis are also discussed based on the characteristics of metal/TiO2 including X-ray differential (XRD) patterns, Brunquer Emmett Teller (BET) specific area analysis, and Ultra Violet (UV)-Vis absorption spectra.     

Discoloration of methylene blue and wastewater from a plant by a Fe/Cu bimetallic system

Using a Fe/Cu bimetallic system (Fe/Cu system), the discoloration of both methylene blue in aqueous solution and the colored wastewater from a plant was investigated under the anaerobic condition in batch or continuous reactors. Results show that the Fe/Cu system effectively removed the color with over 88% of color removal efficiency for both methylene blue solution and the wastewater from the plant in batch test. Color removal efficiencies increased rapidly with Fe/Cu dosage and reaction time, respectively, at initial time and slowly to stable values. Optimum pH was neutral range. In addition, in continuous test it also removed the color of the wastewater from the plant with 63% of discoloring efficiency under the condition of 2 h of hydraulic retention time and neutral range of pH (7.0-8.3). High discoloring efficiencies with low chemical oxygen demand removal efficiencies were found in all experiments. The reduction of chromophores in pollutants was the main mechanism of the discoloration in the Fe/Cu system.     

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

Catalytic oxidation of pentachlorophenol in contaminated soil suspensions by Fe+3-resin/H2O2

Pentachlorophenol (PCP) is a wood preserving agent that is commonly found in contaminated soils at wood treatment sites. The catalytic properties of Fe+3-resin for the oxidation of PCP in aqueous solution and soil suspension with H2O2 were tested. Batch tests in aqueous solution were performed at various dosages of catalyst and H2O2, and reaction temperatures. The results showed that the oxidation of PCP in aqueous solution depends on the dose of H2O2 and the temperature. Essentially complete oxidation of 100 mgl(-1) PCP was obtained with 0.5% Fe+3-resin catalyst, 0.1 M H2O2 and at a reaction temperature of 80 degrees C. The oxidation of PCP achieved in three different soil suspensions was more than 94% within 30-50 min. Moreover, it was demonstrated that the same Fe+3-resin could be reused for at least six cycles of PCP oxidation in soil solutions without loss in efficiency unless the pH of the reaction falls below 5. It was proposed that the loss in used Fe+3-resin catalyst activity could be related to the leaching of Fe+3 at low pH.     

Enhanced Photocatalysis of Pentachlorophenol by Metal-Modified Titanium (IV) Oxide

The effects of four metals (Ag, Au, Pt, and Cu) doped on TiO₂ on the photocatalysis of pentachlorophenol (PCP) were investigated. The results of this study indicated that all four metals-doped TiO₂ catalysts were able to enhance the efficiency of PCP photocatalysis with an optimum metallic content of 0.1 wt%. For the metal-doped TiO₂ samples (Au, Pt, and Cu), the patterns of light absorption were significantly extended toward visible light spectra in the wavelengths between 400 and 800 nm. The photocatalysis of PCP was pH dependent with the maximum degradation rate achieved in the solution at pH 3. The formation of chloride ion corresponded with the concentration of PCP degraded which confirmed that dechlorination was the major pathway of PCP photocatalysis. The overall toxicities of PCP samples were reduced with the extension of light exposure using the microtox test. The results of PCP photocatalysis are also discussed based on the characteristics of metal/TiO₂ including X-ray differential (XRD) patterns, Brunquer Emmett Teller (BET) specific area analysis, and Ultra Violet (UV)-Vis absorption spectra.     

微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

高岭土负载纳米铁镍双金属去除水中偶氮染料直接耐晒黑G

采用液相还原法制备焙烧高岭土负载纳米铁镍双金属（CK-Fe/Ni）。考察了在不同条件下,如pH、投加量、初始浓度、温度等,对负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的影响及动力学研究。结果表明：在pH=9.49、温度为30℃、负载型纳米铁镍双金属的投加量为1.05 g/L、搅拌速度为60 r/min,经过20 min反应后,负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的去除率达到了99.98%。吸附和电镜表征结果表明,作为载体的焙烧高岭土起着吸附直接耐晒黑G和分散纳米铁镍双金属颗粒的作用导致反应活性提高。降解动力学数据表明,负载型纳米铁镍双金属对直接耐晒黑G的降解过程符合伪一级反应动力学规律,速率常数k随负载型纳米铁镍双金属的投加量的增加而提高,表观活化能为19.72 kJ/mol。最后,利用高岭土负载纳米铁镍双金属对废水处理,结果表明,负载型纳米铁镍双金属在实际废水中对直接耐晒黑G的去除率达到了99.98%。     

Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn

Groundwater and wastewater contaminated with chlorinated organic compounds (COCs) can be treated with zero-valent metals. The practicality of this treatment method depends on the reduction rates of the target compounds and their byproducts. In this study, nano-scale Fe and Fe/Ni particles were synthesized so that they could be used to rapidly degrade carbon tetrachloride (CT) and chloroform (CF). Their BET surface areas were around two orders higher than those of commercial micro-scale Fe and Zn particles. Batch reduction experiments carried out with a metal loading of 2.5 gl(-1) showed that complete reduction of CT by the nano-scale Fe/Ni and Fe particles could be achieved within 20 min and 60 min, respectively. With the commercial micro-scale Fe and Zn particles applied at 125 gl(-1), complete CT reduction could only be achieved after 4h and 1.5h, respectively. Reductions of CT and CF with the nano-scale particles followed pseudo-first-order kinetics, and the specific reaction rate constants with the nano-scale Fe/Ni particles were 2-8 times higher than those of the nano-scale Fe particles. CT was degraded through hydrogenolysis to CF, and subsequently via both complete reduction pathway to methane and hydrogenolysis pathway to dichloromethane (DCM). Significantly more methane was generated with the use of the nano-scale Fe/Ni particles than with the nano-scale Fe particles. While the commercial Zn particles were more reactive than the commercial Fe particles, they failed to transform CT directly into methane, causing accumulation of DCM in the aqueous phase.