Dechlorination of chlorinated methanes by Pd/Fe bimetallic nanoparticles

This paper examined the potential of using Pd/Fe bimetallic nanoparticles to dechlorinate chlorinated methanes including dichloromethane (DCM), chloroform (CF) and carbon tetrachloride (CT). Pd/Fe bimetallic nanoparticles were prepared by chemical precipitation method in liquid phase and characterized in terms of specific surface area (BET), size (TEM), morphology (SEM), and structural feature (XRD). With diameters on the order of 30-50 nm, the Pd/Fe bimetallic nanoparticles presented obvious activity, and were suited to efficient catalytic dechlorination of chlorinated methanes. The effects of some important reaction parameters, such as Pd loading (weight ratio of Pd to Fe), Pd/Fe addition (Pd/Fe bimetallic nanoparticles to solution ratio) and initial pH value, on dechlorination efficiency were sequentially studied. It was found that the maximum dechlorination efficiency was obtained for 0.2 wt% Pd loading. The dechlorination efficiency was observed to increase with increasing Pd/Fe addition. The optimal pH value for dechlorination reaction of chlorinated methanes was about 7. Kinetics of chlorinated methane dechlorination in the catalytic reductive system of Pd/Fe bimetallic particles were investigated. The dechlorination reaction complied with pseudo-first-order kinetics.     

The use of mechanical alloying for the preparation of palladized magnesium bimetallic particles for the remediation of PCBs

The kinetic rate of dechlorination of a polychlorinated biphenyl (PCB-151) by mechanically alloyed Mg/Pd was studied for optimization of the bimetallic system. Bimetal production was first carried out in a small-scale environment using a SPEX 8000M high-energy ball mill with 4-μm-magnesium and palladium impregnated on graphite, with optimized parameters including milling time and Pd-loading. A 5.57-g sample of bimetal containing 0.1257% Pd and ball milled for 3 min resulted in a degradation rate of 0.00176 min⁻¹ g⁻¹ catalyst as the most reactive bimetal. The process was then scaled-up, using a Red Devil 5400 Twin-Arm Paint Shaker, fitted with custom plates to hold milling canisters. Optimization parameters tested included milling time, number of ball bearings used, Pd-loading, and total bimetal mass milled. An 85-g sample of bimetal containing 0.1059% Pd and ball-milled for 23 min with 16 ball bearings yielded the most reactive bimetal with a degradation rate of 0.00122 min⁻¹ g⁻¹ catalyst. Further testing showed adsorption did not hinder extraction efficiency and that dechlorination products were only seen when using the bimetallic system, as opposed to any of its single components. The bimetallic system was also tested for its ability to degrade a second PCB congener, PCB-45, and a PCB mixture (Arochlor 1254); both contaminants were seen to degrade successfully.     

Poly(amino acid)-facilitated electrochemical growth of metal nanoparticles

Poly(amino acids) are natural chelating agents for various metal ions. Zinc ions were encapsulated in situ in a conductive polypyrrole film using polyglutamic acid as a localized complexing agent within the film. The subsequent electrochemical reduction of the metal ions to zero-valent metal leads to the formation of the nanoparticles. The electrochemical approach demonstrated in this report provides facile regeneration of the particles and also prevents aggregation of nanoparticles in the conductive polymeric film. The correlation of the amount of zinc with the thickness of the film indicates that the zinc resides largely in the outer layer of the film. TEM and EDS data show that the nanoparticles formed are composed of zinc and are 18 +/- 7 nm in diameter. The nanoparticle/ polymer composite was used to reduce halogenated organics, indicating its potential usefulness in remediation applications.     

Studies on dechlorination of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) using magnesium/palladium bimetallic system

The aim of our investigation was to compare the rates of dechlorination of DDT using Mg0/Pd4+ system in two different reaction phases, namely, water-acetone and 0.05% biosurfactant in water. Since palladium is expensive and its toxicity effects are not well known we also examined the reuse efficiency of Pd0 immobilized on alumina for dechlorinating DDT. Studies on the dechlorination of DDT in water-acetone (1:1, v/v) and 0.05% biosurfactant phases revealed that the reaction followed second order kinetics and rate of reaction is dependent upon both initial concentrations of the target compound and Mg0/Pd4+. The presence of acid enhanced the rate of reaction by providing protons and preventing passivation of metal that occurs due to deposition of magnesium hydroxide. GC-MS analyses revealed the formation of completely dechlorinated hydrocarbon skeleton of DDT namely, diphenylethane (DPE), as the end product in both reaction phases (water-acetone and 0.05% biosurfactant in water) thereby implying the removal of all five chlorine atoms (three alkyl and two aryl) of DDT. The optimum ratio of water and acetone to facilitate successful dechlorination reaction was found to be 9:1. Results suggested that salt form (K2PdCl6) of palladium had higher potential to dechlorinate DDT as compared to pellet (Pd0-alumina) form (efficiencies of 95 and 36%, respectively, for 100 ppm initial concentration of DDT). We noted that Pd0-alumina pellets could be reused at least four times for successful dechlorination of DDT provided Mg0 granules are present in sufficient quantity. Technical grade DDT (50 ppm) containing significant amounts of DDD was dechlorinated almost completely by the Mg0/Pd4+ (10mg/0.2mg/ml) within 1h in water-biosurfactant phase. Our studies reveal that Mg/Pd system is a promising option due to its high reactivity and its ability to achieve complete dechlorination of DDT. This bimetallic system may be useful for designing indigenous permeable barriers or reactors for the treatment of DDT contaminated water.     

Dechlorination of trichloroethylene in aqueous solution by noble metal-modified iron

Bimetallic particles are extremely interesting in accelerating the dechlorination of chlorinated organics. Four noble metals (Pd, Pt, Ru and Au), separately deposited onto the iron surface through a spontaneous redox process, promoted the TCE dechlorination rate, and the catalytic activity of the noble metal followed the order of Pd>Ru>Pt>Au. This order was found to be dependent on the concentrations of adsorbed atomic hydrogen, indicating that the initial reaction was cathodically controlled. Little difference in the distribution of the chlorinated products for the four catalysts (cis-DCE: 51%; 1,1-DCE: 27%; trans-DCE: 15% and VC: 7%) was observed. The chlorinated by-products accumulated in both Pt/Fe and Au/Fe (10.3% and 2.5% of the transformed TCE, respectively), but did not accumulate in Pd/Fe and Ru/Fe. Ru/Fe was further examined as an economical alternative to Pd/Fe. The 1.5% Ru/Fe was found to completely degrade TCE within 80 min. Considering the expense, the yield of chlorinated products and the lifetime of a reductive material, Ru provides a potential alternative to Pd as a catalyst in practical applications.     

Catalytic dechlorination of polychlorinated biphenyls in soil by palladium-iron bimetallic catalyst

Pd/Fe bimetallic particles were synthesized by chemical deposition and used to dechlorinate 2,2',4,5,5'-pentachlorobiphenyl in soil. Batch experiments demonstrated that the Pd/Fe bimetallic particles could effectively dechlorinate 2,2',4,5,5'-pentachlorobiphenyl. Dechlorination was affected by several factors such as reaction time, Pd loading, the amount of Pd/Fe used, initial soil pH, and 2,2',4,5,5'-pentachlorobiphenyl concentration. The results showed that higher Pd loading, higher dosage of Pd/Fe, lower initial concentration of 2,2',4,5,5'-pentachlorobiphenyl and slightly acid condition were beneficial to the catalytic dechlorination of 2,2',4,5,5'-pentachlorobiphenyl. The degradation of 2,2',4,5,5'-pentachlorobiphenyl, catalyzed by Pd/Fe followed pseudo-first-order kinetics.     

Growth of carbon nanostructures on carbonized electrospun nanofibers with palladium nanoparticles

This paper studies the mechanism of the formation of carbon nanostructures on carbon nanofibers with Pd nanoparticles by using different carbon sources. The carbon nanofibers with Pd nanoparticles were produced by carbonizing electrospun polyacrylonitrile (PAN) nanofibers including Pd(Ac)(2). Such PAN-based carbon nanofibers were then used as substrates to grow hierarchical carbon nanostructures. Toluene, pyridine and chlorobenzine were employed as carbon sources for the carbon nanostructures. With the Pd nanoparticles embedded in the carbonized PAN nanofibers acting as catalysts, molecules of toluene, pyridine or chlorobenzine were decomposed into carbon species which were dissolved into the Pd nanoparticles and consequently grew into straight carbon nanotubes, Y-shaped carbon nanotubes or carbon nano-ribbons on the carbon nanofiber substrates. X-ray diffraction analysis and transmission electron microscopy (TEM) were utilized to capture the mechanism of formation of Pd nanoparticles, regular carbon nanotubes, Y-shaped carbon nanotubes and carbon nano-ribbons. It was observed that the Y-shaped carbon nanotubes and carbon nano-ribbons were formed on carbonized PAN nanofibers containing Pd-nanoparticle catalyst, and the carbon sources played a crucial role in the formation of different hierarchical carbon nanostructures.     

Microwave-assisted synthesis of palladium nanocubes and nanobars

Microwave was employed in the shape-controlled synthesis of palladium nanoparticles. Palladium nanocubes and nanobars with a mean size of about 23.8 nm were readily synthesized with H₂PdCl₄ as a precursor, tetraethylene glycol (TEG) as both a solvent and a reducing agent in the presence of PVP and CTAB in 80 s under microwave irradiation. The structures of the as-prepared palladium nanoparticles were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and ultraviolet-visible (UV-vis) absorption spectroscopy. The formation of PdBr₄²⁻due to the coordination replacement of the ligand Cl⁻ ions in PdCl₄²⁻ ions by Br⁻ ions in the presence of bromide was responsible for the synthesis of Pd nanocubes and nanobars. In addition, a milder reducing power, a higher viscosity and a stronger affinity of TEG were beneficial to the larger sizes of Pd nanocubes and nanobars.     

Dechlorination of chlorinated phenols by catalyzed and uncatalyzed Fe(0) and Mg(0) particles.

Uncatalyzed, and palladium-catalyzed Fe(0) and Mg(0) systems were examined for their efficiencies of dechlorination of 2.86 mM 4-chlorophenol (4-CP), 2.52 mM 2,6-dichlorophenol (2,6-DCP), 3.03 mM 2,4,6-trichlorophenol (2,4,6-TCP), and 2.48 mM pentachlorophenol (PCP) in 50/50 (v/v) 2-propanol/water under room temperature and pressure conditions. Previous investigators have found that PCP is extremely recalcitrant under these conditions. In this investigation, complete dechlorination of 5.0 ml of 2.48 mM PCP was observed for 1.0 g of 2659 ppm Pd/Mg (20 mesh) after 48 h. The only detectable products were cyclohexanol and cyclohexanone at 25% yield. No other chlorinated or otherwise products were observed by mass spectral analysis. It is hypothesized that volatile low molecular weight species were formed from the Pd/Mg dechlorination of PCP. Under conditions of equal surface area (0.0786 m2), the approximate order of PCP dechlorination power of these systems followed as 2659 ppm Pd/Mg>319 ppm Pd/Mg>Mg approximately 4856 ppm Pd/Fe>Fe. Degradation of the other chlorinated phenols by all metallic systems was more facile than PCP.     

氟硅橡胶复合膜透气性的研究

通过把氟硅橡胶填充进多孔微滤支撑体来制备聚偏氟乙烯(PVDF)和氟硅橡胶(FVMQ)的复合膜.并研究了支撑层孔径和白炭黑填料对FVMQ复合膜透气性能的影响.自制气室,测试了FVMQ复合膜对H2、Ar和N2的渗透特性.结果表明,PVDF膜孔径越大FVMQ复合膜的渗透速率就越快,在FVMQ溶液中加入白炭黑填料却降低了膜的渗透速率.支撑层孔径对膜渗透性能的影响比填料的影响显著.对FVMQ复合膜透气性的研究为其在气体分离方面应用奠定基础.     

Optical study of the reduction of hexavalent chromium by iron-based nanoparticles

In this paper, a simple method was presented to measure the concentration change in the Cr(VI)-contained waste water during treatment by nanoparticles, based on its optical absorption spectral evolution which exhibits a good linear relationship between the absorbance of the peak at 348 nm and Cr6+ ion concentration. The iron and Fe/Pd bimetal nanoparticles were prepared and used for removal of Cr6+ in waste water. It has been found that presented method for concentration determination based on optical spectral evolution is effective and flexible. The nanoparticles have higher efficiency than normal iron powders and Fe/Pd bimetallic nanoparticles show faster removal of the Cr6+ than iron nanoparticles. The study is of importance in environmental remediation or pollution treatment of heavy metal ions in water and even soil.     

Dechlorination of hexachlorocyclohexanes with alkaline 2-propanol and a palladium catalyst

Hexachlorocyclohexane isomers (alpha-, beta-, gamma- and delta-HCH) were dechlorinated in 2-propanol by means of stoichiometric reaction with NaOH and subsequent catalytic dechlorination over a supported palladium catalyst (Pd/C). When the HCH isomers (2-10 mmol/l) were reacted with a molar excess of NaOH ([NaOH]/[HCH]>9) in 2-propanol, transformation of alpha-, gamma- and delta-HCH to trichlorobenzenes (TCBs) was complete within 5 min at room temperature, but beta-HCH was less reactive. Analysis of TCB isomers produced from individual HCH isomers showed that 1,2,4-TCB was always predominant (70-90% of the product) and 1,2,3-TCB and 1,3,5-TCB were minor products. The produced TCBs were dechlorinated by subsequently adding Pd/C to the alkaline 2-propanol solution and heating at 55 degrees C for 3 h, resulting in the formation of benzene in high yield (>80%). Technical-grade HCH, which contains these four isomers, was successfully dechlorinated with NaOH and Pd/C at 55 degrees C.     

直接微滤用于舰船反渗透海水淡化预处理的可行性研究

采用国产聚偏氟乙烯中空纤维膜,研究了直接微滤工艺用于舰船反渗透海水淡化预处理的可行性.实验结果表明,直接微滤预处理系统采用直接过滤20min→气水双洗30s→滤过水反洗30s→排污5s的运行条件处理高浊度海水时,滤过水淤泥密度指数(SDI)≤2.9,浊度<0.9NTU;滤膜抗污染性能较强,当系统跨膜压差≥37kPa时,采用次氯酸钠和盐酸化学清洗,跨膜压差可恢复到低压水平.直接微滤预处理系统结构紧凑,操作方便,出水水质稳定,符合我国舰船装备研制相关标准的要求,可用于舰船反渗透海水淡化预处理.     

Reductive destruction and decontamination of aqueous solutions of chlorinated antimicrobial agent using bimetallic systems

Palladium, ruthenium and silver were investigated as catalysts for the dechlorination of dichlorophen (DCP, 2,2'-methylenebis(4-chlorophenol)), an antimicrobial and anthelmintic agent largely used as algicide, fungicide and bactericide. Experiments were undertaken under oxic and anoxic conditions for experimental durations up to 180 min (3h). The anoxic conditions were achieved by purging the solutions with nitrogen gas. Reactions were performed in a 12+/-0.5 mg L(-1) DCP solution (V=20 mL) using 0.8 g of Fe(0) (40 g L(-1)). Along with micrometric Fe(0), five Fe(0)-plated systems were investigated: Pd (1%), Ru (0.01%), Ru (0.1%), Ru (1%) and Ag (1%). Metal plating was controlled by atomic absorption spectroscopy. DCP degradation was monitored using: (i) two HPLC devices, (ii) ion chromatography, (iii) UV and fluorescence spectrophotometry. Results indicated: (i) total dechlorination with Fe/Pd, (ii) partial dechlorination (40%) with Fe/Ru, and no reaction with Fe/Ag. DCP is vanished completely after 90 min of contact with Fe/Pd following a first order kinetic. The observed degradation rate k(obs) was about (3.98+/-0.10)x10(-2)min(-1), the calculated half-life t(1/2) about 17.4+/-0.9 min and a t(50) about 10.1+/-0.5 min. A DCP degradation pathway map was also proposed.     

Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene

Palladium (Pd) nanoparticle catalysts were successfully synthesized within an aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping ligand which offers a green alternative to conventional nanoparticle synthesis techniques. The CMC-stabilized Pd nanoparticles were subsequently dispersed within support materials using the incipient wetness impregnation technique for utilization in heterogeneous catalyst systems. The unsupported and supported (both calcined and uncalcined) Pd nanoparticle catalysts were characterized using transmission electron microscopy, energy dispersive x-ray spectrometry, x-ray diffraction, and Brunauer-Emmett-Teller surface area measurement and their catalytic activity toward the hydrodechlorination of trichloroethylene (TCE) in aqueous media was examined using homogeneous and heterogeneous catalyst systems, respectively. The unsupported Pd nanoparticles showed considerable activity toward the degradation of TCE, as demonstrated by the reaction kinetics. Although the supported Pd nanoparticle catalysts had a lower catalytic activity than the unsupported particles that were homogeneously dispersed in the aqueous solutions, the supported catalysts retained sufficient activity toward the degradation of TCE. In addition, the use of the hydrophilic Al(2)O(3) support material induced a mass transfer resistance to TCE that affected the initial hydrodechlorination rate. This paper demonstrates that supported Pd catalysts can be applied to the heterogeneous catalytic hydrodechlorination of TCE.     

纳米钯/铁双金属颗粒对一氯乙酸的脱氯

为了提高零价铁对氯代有机物还原脱氯的性能,采用还原沉淀法制备了纳米钯/铁双金属颗粒.利用X射线衍射(XRD)、X射线荧光光谱(XRF)、扫描电子显微镜(SEM)、透射电镜(TEM)、以及BET-N2比表面积法对纳米钯/铁双金属颗粒进行了表征.结果表明,制备的纳米钯/铁双金属颗粒中Fe主要以α-Fe0形式存在.纳米钯/铁双金属颗粒的直径约为30～50nm,比表面积约51m2/g.纳米钯/铁双金属颗粒对一氯乙酸还原脱氯的脱氯率是还原铁粉和纳米铁粉对一氯乙酸还原脱氯的脱氯率的7.9倍和1.7倍.     

Dechlorination of 3,3′,4,4′-tetrachlorobiphenyl in aqueous solution by hybrid Fe0/Fe3O4 nanoparticle system

The kinetics and efficiency of 3,3′,4,4′-tetrachlorobiphenyl (PCB77) degradation in aqueous solution by hybrid Fe⁰/Fe₃O₄ nanoparticle system were investigated. The results showed that nano-sized Fe⁰ and Fe₃O₄ could efficiently degrade PCB77, and the residual rate of PCB77 by nano-sized Fe⁰ and Fe₃O₄ were 67.70% ± 0.42% and 82.26% ± 2.96%, respectively after 240 min of reaction (for 5 mg·L^?1 PCB77 and 5 g·L^?1 nanoparticles). The combined use of nanoscale Fe⁰ and Fe₃O₄ could enhance the degradation of PCB77. The dose ratios of nano-sized Fe⁰ and Fe₃O₄ significantly affected the PCB77 degradation rate. At Fe⁰/Fe₃O₄ ratios of 1:0.1, 1:0.2 and 1:1, the residual rates of PCB77 were 6.46%, 10.23% and 38.20%, respectively. The PCB77 degradation efficiency was also greatly affected by solution pH, and was maximised at pH 6.8. The degradation of PCB77 by Fe⁰/Fe₃O₄ nanoparticle was a dechlorination process, and the chlorion concentration increased with the decreasing residual rate of PCB77 accordingly. Fe₃O₄ provided Fe²⁺ and Fe³⁺ for enhancing the PCB77 degradation by nanoscale Fe⁰, suggesting a synergy between Fe⁰ and Fe₃O₄.     

TiO_2动态改性膜应用于MBR的研究

采用二氧化钛(TiO_2)纳米粒子对聚偏氟乙烯中空纤维膜微滤膜(PVDF MF,0.1μm)和实验室自制聚砜中空纤维膜超滤膜(PSF UF,0.05μm)进行表面亲水改性,以期提高膜的抗污染能力.采用膜接触角、纯水通量、出水TOC、膜压差和扫描电子显微镜(SEM)进行表征了TiO_2动态膜的性能.将TiO_2纳米颗粒改性后的PVDF MF和PSF UF膜应用于膜生物反应器(MBR)处理模拟焦化废水(TOC=500 mg/L),考察了其对MBR过滤性能的影响.实验结果表明,改性后膜的水接触角明显减小,亲水性增强,TMP升高速率明显降低,模拟焦化废水,TOC的去除率平均可达95%,经返洗及次氯酸钠清洗后膜表面TiO_2层外观没有明显变化.改性后的膜组件较显著地增加了MBR的膜抗污染的优势,且具有一定的稳定性.因此,将TiO_2动态改性耐污染膜应用于MBR是可行的.     

Selective hydrogenation of acetylene over egg-shell palladium nano-catalyst

A novel egg-shell Pd/PHSNs nano-catalyst was prepared by a wet impregnation method using self-synthesized porous hollow silica nanoparticles (PHSNs) as support and applied in selective hydrogenation of acetylene to remove acetylene from the ethylene feed. By controlling the preparing conditions and calcining temperature, the active metal particles were loaded evenly on the support with a size about 5 nm. Compared with conventional catalysts prepared with solid silica nanoparticles, solid Al2O3 millispheres and a commercial catalyst, the Pd/PHSNs catalyst showed higher acetylene conversion rates at same reaction temperatures, and the porous hollow nano structure of PHSNs allowed smoother diffusion of ethylene molecules within the catalyst matrix so that ethylene could migrate away from the active sites in time to avoid turning into ethane, which resulted in superior ethylene selectivity at high acetylene conversion rates.     

Synthesis of size-controlled Fe3O4@SiO2 magnetic nanoparticles for nucleic acid analysis

We present a systematic study on the preparation, characteration and potential application of Fe3O4 and Fe3O4@SiO2 nanoparticles. Fe3O4 nanoparticles of controllable diameters were successfully synthesized by solvothermal system with tuning pH. The magnetic properties of nanoparticles were measured by vibration sample magnetometer. Fe3O4@ SiO2 nanoparticles were obtained via classic St?ber process. Streptavidin coated Fe3O4@SiO2 nanoparticles were prepared by covalent interaction. The quantity of streptavidin bound to nanoparticles was determined by UV-Vis spectrometer. To evaluate the binding efficiency and capacity of nucleic acid on nanoparticles, the capture of biotinylated oligonucleotide on streptavidin coated Fe3O4@SiO2 nanoparticles at different concentration was estimated by fluorescence detection. Both Fe3O4 and Fe3O4@SiO2 nanoparticles exhibited well crystallization and magnetic properties. The maximal amount of streptavidin immobilized onto the Fe3O4@SiO2 nanoparticles was 29.3 microg/mg. The saturation ratio of biotinylated oligonucleotides captured on streptavidin coated Fe3O4@SiO2 nanoparticles was 5 microM/mg within 20 minutes, indicating that FeO4@SiO2 nanoparticles immobilized by streptavidin were excellent carriers in nucleic acid analysis due to their convenient magnetic-separation property. Therefore, the synthesized Fe3O4 and Fe3O4@SiO2 nanoparticles with controllable size and high magnetic saturation have shown great application potentials in nucleic acid research.