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.     

Rapid and complete dechlorination of PCP in aqueous solution using Ni-Fe nanoparticles under assistance of ultrasound

The Ni-Fe bimetallic particles have been laboratory prepared using sodium borohydride (NaBH4) as the reductant to reduce Ni2+ and Fe2+ in aqueous solution simultaneously, and characterized by TEM, XRD, BET and XPS. The particles were proved to be nanoscale amorphous alloy with an average diameter of about 30 nm and a BET surface area of 20.9 m2 g(-1). Experiments for dechlorination of pentachlorophenol (PCP) by the Ni-Fe bimetallic nanoscale particles in aqueous solutions were carried out under the enhancement of ultrasound. Major factors that influence the dechlorination efficiency, such as initial pH value, Ni content in the Ni-Fe particles, and output power of ultrasonic irradiation, were investigated. The results indicated that Ni-Fe nanoscale bimetallic particles were very effective for the dechlorination of PCP. Dechlorination efficiency was 46% in 30 min under the optimal condition without assistance of ultrasound, whereas it increased to 96% when ultrasonic irradiation was present. Initial pH value showed apparent effect on the dechlorination. As the pH varied from acidic condition to neutral condition, the dechlorination efficiency decreased dramatically. In addition, the dechlorination efficiency was improved with increased Ni/Fe ratio and ultrasonic output power. Less chlorinated phenols including tetrachlorophenol, trichlorophenol, dichlorophenol, monochlorophenol were formed during the initial reaction, and phenol was determined by GC-MS as sole product in the end of reaction.     

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。     

氢自养生物还原去除地下水中对硝基氯苯（p-NCB）的实验研究

采用批式实验讨论了氢自养还原菌在厌氧条件下,利用氢气作为电子供体还原地下水中对硝基氯苯的可行性及其影响因素。结果表明,氢自养菌能利用氢气生物还原对硝基氯苯,并产生中间产物对氯苯胺,继而进一步还原脱氯产生苯胺,该过程可提高对硝基氯苯的可生化性。对硝基氯苯在初始阶段还原速率较快,最高去除速率达到610μg/（L.d）,随后逐渐降低达到稳定。影响因素实验表明,在一定浓度范围内提高对硝基氯苯浓度对其去除率影响较小,但硝基进一步还原和脱氯效果降低;氢自养菌还原硝基氯苯的最适宜pH值在7.0~8.0之间;水中的硝酸盐和对硝基氯苯对电子供体存在竞争,硝酸盐反硝化对对硝基氯苯还原具有抑制作用。     

The complete dechlorination of DDT by magnesium/palladium bimetallic particles

The complete dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) by a magnesium/palladium bimetallic system has been accomplished. The reaction takes place under ambient temperature and pressure and mild reaction conditions requiring only 0.25 g of magnesium and 0.3% palladium (wt/wt) to drive the dechlorination of 100 microg DDT (50 ppm in 2 ml). The process is both rapid and complete requiring less than 10 min to attain total dechlorination within the detection limit (approximately 10 pg for DDT) of electron capture detection gas chromatography (GC-ECD). The major product formed, as deduced from mass spectrometry (GC-MS) is the hydrocarbon skeleton, 1,1-diphenylethane. This technology may allow for the development of an economic and environmentally benign method of DDT remediation.     

Catalytic degradation of chlorothalonil in water using bimetallic iron-based systems

Modified zero valent iron (MZVI) was used to study the transformation of a chlorothalonil (CLT) solution and the variation of the observed degradation rate of the reduction reactions. This was carried out when transition metals e.g. Pd, Cu and Co plated on the surface of micrometric iron particles (< 150 microm) were used as reducing catalytic agents for pesticide removal. Reactions were undertaken under both oxic and anoxic conditions in the presence and the absence of a phosphate buffer solution (PBS). Results of batch studies in nitrogen sparged solutions revealed that incomplete slow dechlorination merely occurred with zero valent iron (ZVI), however, complete rapid dechlorination reactions took place with MZVI especially Fe/Pd. Dechlorination was depicted by studying UV absorbance and MS spectra of CLT and all corresponding by-products. Typical blue shifts (deltalambda = 4-6 nm/chlorine atom) were observed at the same time as chlorine cluster isotopes disappeared. After the plating process, metal loading was controlled by analyzing the remaining metal in the solution by atomic absorption spectroscopy. Experiments showed that CLT degradation mechanism is faster in nitrogen sparged solutions in the absence of PBS. Time needed for complete removal of 2.08 +/- 0.19 microM CLT solution was about 2 h when experiments were conducted with ZVI (t1/2 = 15.0 min) and about 10 min when the reaction was carried out under the same conditions with Fe/Pd 1% (t1/2 = 1.0 min). Degradation rates for all bimetallic systems were determined showing that Pd is the more exciting catalytic transition metal followed by Cu and Co. Furthermore, MZVI method showed obvious advantage to traditional CLT treatment methods.     

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.     

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.     

Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2′azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron–palladium (Fe–Pd) and titania (TiO₂) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe–Pd and nitrogen-doped TiO₂ nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe–Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.     

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.     

Effects of anions on the kinetics and reactivity of nanoscale Pd/Fe in trichlorobenzene dechlorination

Influences of anionic co-solutes on dechlorination of 1,2,4-trichlorobenzene (124TCB) by the nanoscale Pd/Fe particles were investigated in batch experiments in the presence of an anionic solute such as nitrate, nitrite, perchlorate, phosphate, carbonate, silica, sulfate, sulfite, or sulfide. Based on the extent of inhibitory effects on the 124TCB dechlorination, the anions can be ranked in the order of: control≈sulfate≈silica相似文献   

纳米Pd／Fe双金属颗粒对单氯酚及二氯酚的还原脱氯

采用改进液相化学还原法制备纳米Pd／Fe双金属颗粒，研究其钯化率为0．045％和0．135％的条件下分别对3种单氯酚（2-CP、3-CP和4-CP）和3种二氯酚（2，3-DCP、2，4-DCP和2，6-DCP）的脱氯反应。结果表明，合成的纳米Pd／Fe颗粒分散性良好，粒径分布介于25～40nm。纳米Pd／Fe双金属颗粒对单氯酚及二氯酚具有良好的去除效果，3种单氯酚和3种二氯酚的脱氯难易程度分别为2-CP〉4-CP〉3-CP和2，6-DCP〉2，4-DCP〉2，3-DCP，脱氯反应均符合拟一级反应动力学方程。通过还原脱氯实验揭示了分子中氯原子的化学环境对还原脱氯过程具有明显影响。     

Structure relationship for catalytic dechlorination rate of dichlorobenzenes in water

Three isomers of dichlorobenzene (o-, m- and p-DCB) were dechlorinated by Pd/Fe catalyst in aqueous solutions through catalytic reduction. The dechlorination reaction took place on the surface site of the catalyst via a pseudo-first-order kinetics, and resulted in benzene as the final reduction product. The rate constants of the reductive dechlorination for the three dichlorobenzenes (DCBs) in the presence of Pd/Fe as a catalyst were measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy of the formation of DCBs. The reaction rate constant for o-, m- and p-DCBs in the presence of 0.020% (w/w) Pd/Fe at 25 °C was determined to be 0.0213, 0.0223, and 0.0254 min⁻¹, respectively. While the activation energy of each dechlorination reaction was measured to be 102.5, 96.6 and 80.0 kJ mol⁻¹ for o-, m- and p-DCBs, respectively. The results demonstrated that p-DCBs were reduced more easily than o- or m-DCBs, and the order of the tendency of the dechlorination was p-DCB > m-DCB > o-DCB. The presented data show the catalytic reduction using Pd/Fe as a catalyst is a fast and easy approach for the dechlorination of DCBs.     

Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe(zero-valent) particles supported on chitosan and silica

In this study, nanoscale Pd-Fe particles, with diameters less than 100 nm, were synthesized and dispersed over the chitosan and silica supports. Three different Pd-Fe particles were synthesized, namely 0.1% Pd-Fe, 0.5% Pd-Fe and 1.0% Pd-Fe. SEM images confirmed that the Pd-Fe particles were dispersed over the surface of the supports while SEM-EDX confirmed evenly distribution of Pd over Fe(zero-valent). alpha-Fe(zero-valent) crystallites were identified by means of XRD and observed in TEM. Reductive dechlorinations of 1,2,4-trichlorobenzene (1,2,4-TCB) with the nanoscale Pd-Fe/chitosan and Pd-Fe/silica were carried out in the batch experiment system. Disappearance of the parent species and formation of the reaction intermediates and end product were monitored at discrete times. The results show that the nano-scale Pd-Fe particles were able to completely dechlorinate the chlorinated benzenes within a very short timescale. Complete dechlorinations of 1,2,4-TCB to benzene were achieved within 60 min with the 1.0% Pd-Fe/chitosan and within 100 min with the 1.0% Pd-Fe/silica. Reaction rates were observed to increase with increasing Pd content of the Pd-Fe/support. The reactions apparently followed pseudo-first-order kinetics with respect to the 1,2,4-TCB transformation. A kinetic model is constructed to fit the experimental results for the reactions, enabling identification of the major and minor dechlorination pathways of 1,2,4-TCB. The model suggests that the 1,2,4-TCB transformation mainly followed the primary pathway of direct reductive dechlorination to benzene and secondary pathway of sequential hydrogenolysis to 1,2-dichlorobenzene (1,2-DCB) and then chlorobenzene (CB) or benzene.     

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.     

Hydrodechlorination of polychlorinated biphenyls in contaminated soil from an e-waste recycling area,using nanoscale zerovalent iron and Pd/Fe bimetallic nanoparticles

Soil pollution by polychlorinated biphenyls (PCBs) arising from the crude disposal and recycling of electronic and electrical waste (e-waste) is a serious issue, and effective remediation technologies are urgently needed. Nanoscale zerovalent iron (nZVI) and bimetallic systems have been shown to promote successfully the destruction of halogenated organic compounds. In the present study, nZVI and Pd/Fe bimetallic nanoparticles synthesized by chemical deposition were used to remove 2,2′,4,4′,5,5′-hexachlorobiphenyl from deionized water, and then applied to PCBs contaminated soil collected from an e-waste recycling area. The results indicated that the hydrodechlorination of 2,2′,4,4′,5,5′-hexachlorobiphenyl by nZVI and Pd/Fe bimetallic nanoparticles followed pseudo-first-order kinetics and Pd loading was beneficial to the hydrodechlorination process. It was also found that the removal efficiencies of PCBs from soil achieved using Pd/Fe bimetallic nanoparticles were higher than that achieved using nZVI and that PCBs degradation might be affected by the soil properties. Finally, the potential challenges of nZVI application to in situ remediation were explored.     

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.     

Destruction of lindane and atrazine using stabilized iron nanoparticles under aerobic and anaerobic conditions: effects of catalyst and stabilizer

Highly stable Fe-Pd bimetallic nanoparticles were prepared with 0.2% (w/w) of sodium carboxylmethylcellulose (CMC) as a stabilizer. The effectiveness of the stabilized Fe-Pd nanoparticles was studied for degradation of two chlorinated pesticides (lindane and atrazine) under aerobic and anaerobic conditions. Batch kinetic tests showed that under anaerobic condition the nanoparticles can serve as strong electron donors and completely reduce 1 mgl(-1) of lindane at an iron dose of 0.5 gl(-1) or 1mg l(-1) of atrazine with 0.05 gl(-1) iron with a trace amount (0.05-0.8% of Fe) of Pd as a catalyst. In contrast, under aerobic condition, the nanoparticles can facilitate Fenton-like reactions, which lead to oxidation of 65% of lindane under otherwise identical conditions. Under aerobic condition, the presence of CMC reduced the level of hydroxyl radicals generated from the nanoparticels by nearly 50%, and thus, inhibited the oxidation of the contaminants. While the particle stabilization greatly enhanced the anaerobic degradation, it did not appear to be beneficial under aerobic condition. The degradation rate was progressively enhanced as the Pd content increased from 0.05% to 0.8% of Fe, and the catalytic effect of Pd was more significant under anaerobic condition. Under anaerobic condition, lindane is degraded via dihaloelimination and dehydrohalogenation, whereas atrazine is by reductive dechlorination followed by subsequent reductive dealkylation. Under aerobic condition, reactive oxygen species and hydroxyl radicals from the iron nanoparticles are responsible for oxidizing the pesticides. Lindane is oxidized via dechlorination/dehydrohalogenation, whereas atrazine is destroyed through dealkylation of the alkylamino side chain.