Mechanism and influence factors of 2,4-D dechlorination by sodium citrate-activated bimetallic palladium-zero valent iron nanoparticles

Nanoscale zero-valent iron (nZVI) has high removal efficiency and strong reductive ability to organic contaminants, but this reactivity soon ceases and is attributed to rapid passivation of the nZVI surface due to the formation of iron oxides. In the present study, bimetallic palladium-zero valent iron nanoparticles were activated with sodium citrate (SC-nPd/Fe) to enhance 2,4-D dechlorination from aqueous solutions. FTIR and XRD analyses showed that there was no passivation layer on the surface of nZVI after the addition of SC, and XPS analysis confirmed the nZVI after the reaction still maintained high reactivity and surface Pd ratio. The existence of SC facilitated the transfer of electrons from Fe⁰ to contaminants, thus accelerating the reductive dechlorination of 2,4-D. The dechlorination efficiency of 2,4-D on nPd/Fe was only 56.4% in 210 min, while complete dechlorination could be achieved on SC-nPd/Fe under the same conditions, and simultaneously 97.1% of phenoxyacetic acid (PA) was generated. Moreover, the effect of reaction conditions on the dechlorination such as Pd ratio, SC dosage, initial pH and temperature was also investigated, and it was well described by pseudo-first-order kinetic model. In particular, The chelating abilities of SC is similar to EDTA, but it is an environmentally-friendly chelating agent. Findings from the present study suggested that the SC could be a promising substitute for application in the remediation of 2,4-D contained water.     

Catalytic Dechlorination of Chlorobenzene in Water by Pd／Fe System

Chlorobenzene was dechlorinated by Pd/Fe bimetallic system in water through catalytic reduction. The dechlorination rate increases with increase of bulk loading of Pd due to the increase of both the surface loading of the Pd and the total surface area. For conditions with 0.005% Pd/Fe, 45% dechlorination efficiency was achieved within 5 h. The dechlorinated reaction is believed to take place on the bimetal surface in a pseudo-first-order reaction, with the rate constant being 0.0043 min^-1.     

Direct electrochemical oxidation of a pesticide, 2,4-dichlorophenoxyacetic acid,at the surface of a graphite felt electrode: Biodegradability improvement

Pesticides’ biorecalcitrance can be related to the presence of a complex aromatic chains or of specific bonds, such as halogenated bonds, which are the most widespread. In order to treat this pollution at its source, namely in the case of highly concentrated solutions, selective processes, such as electrochemical processes, can appear especially relevant to avoid the possible generation of toxic degradation products and to improve biodegradability in view of a subsequent biological mineralization. 2,4-D was found to be electroactive in oxidation, but not in reduction, and the absence of hydroxyl radicals formation during the electrochemical step was demonstrated, showing that the pretreatment can be considered as a “direct” electrochemical process instead of an advanced electrochemical oxidation process. The presence of several degradation products in the oxidized effluent showed that the pretreatment was not as selective as expected. However, the relevance of the proposed combined process was confirmed since the overall mineralization yield was close to 93%.     

Development and evaluation of an enzyme-linked immunosorbent assay (ELISA) method for the measurement of 2,4-dichlorophenoxyacetic acid in human urine

An enzyme-linked immunosorbent assay (ELISA) method was developed to quantitatively measure 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. Samples were diluted (1:5) with phosphate-buffered saline containing 0.05% Tween and 0.02% sodium azide, with analysis by a 96-microwell plate immunoassay format. No clean up was required as dilution step minimized sample interferences. Fifty urine samples were received without identifiers from a subset of pesticide applicators and their spouses in an EPA pesticide exposure study (PES) and analyzed by the ELISA method and a conventional gas chromatography/mass spectrometry (GC/MS) procedure. For the GC/MS analysis, urine samples were extracted with acidic dichloromethane (DCM); methylated by diazomethane and fractionated by a Florisil solid phase extraction (SPE) column prior to GC/MS detection. The percent relative standard deviation (%R.S.D.) of the 96-microwell plate triplicate assays ranged from 1.2 to 22% for the urine samples. Day-to-day variation of the assay results was within ±20%. Quantitative recoveries (>70%) of 2,4-D were obtained for the spiked urine samples by the ELISA method. Quantitative recoveries (>80%) of 2,4-D were also obtained for these samples by the GC/MS procedure. The overall method precision of these samples was within ±20% for both the ELISA and GC/MS methods. The estimated quantification limit for 2,4-D in urine was 30 ng/mL by ELISA and 0.2 ng/mL by GC/MS. A higher quantification limit for the ELISA method is partly due to the requirement of a 1:5 dilution to remove the urine sample matrix effect. The GC/MS method can accommodate a 10:1 concentration factor (10 mL of urine converted into 1 mL organic solvent for analysis) but requires extraction, methylation and clean up on a solid phase column. The immunoassay and GC/MS data were highly correlated, with a correlation coefficient of 0.94 and a slope of 1.00. Favorable results between the two methods were achieved despite the vast differences in sample preparation. Results indicated that the ELISA method could be used as a high throughput, quantitative monitoring tool for human urine samples to identify individuals with exposure to 2,4-D above the typical background levels.     

Kinetics and Mechanism of Dechlorination of o-Chlorophenol by Nanoscale Pd／Fe

IntroductionTherehasbeenagrowinginterestintheuseofzero valentironforthetreatmentofchlorinatedor ganiccompounds(COCs)inwaterandgroundwater .Thestudieshavebeenfocusedonsuchcompoundsascarbontetrachloride ,trichloroethene ,pesticidesandtherelatedcompounds[1— 7] .Whenironisincontactwithalessreductivemetalsuchaspalladiumwhosecomplexhasbeenusedtohydrogenatenitroben zene[8] ,themetalcouplecanformgalvaniccells .ThisledtothediscoveryofaPd/Febimetalliccomplexofwhichpalladiumservesasacatalystandironasa…     

Reductive dechlorination of 2,4-dichlorophenol using nanoscale Fe<Superscript>0</Superscript>: influencing factors and possible mechanism

Nanoscale Fe⁰ was synthesized through a reductive method in this paper. The experiments were performed to investigate the reduction of 2,4-dichlorophenol (2,4-DCP) by nanoscale Fe⁰ under different conditions. The pathways for the reduction of 2,4-DCP by nanoscale Fe⁰ were discussed. Batch studies demonstrated that the mechanism includes adsorption, dechlorination and cleavage of the benzene ring. Dechlorination, which occurs after 2,4-DCP molecule is adsorbed on the interface of Fe particle, is an interfacial reaction. One or two chlorine atom can be removed from 2,4-DCP to form 2-chlorophenol, 4-chlorophenol or phenol. As the concentration of 2,4-DCP increased, the relative dechlorination ratio decreased. However, the reduced quantities of 2,4-DCP increased. Temperature can influence dechlorination rate and pathway. Dechlorination is prior to cleavage of the benzene ring at a higher temperature, but at a lower temperature, adsorption may be the main pathway, and cleavage of the benzene ring may be prior to dechlorination. Supported by the National Natural Science Foundation of China (Grant Nos. 50325824, 50678089) and the Excellent Young Teacher Program of MOE.     

在线GPC-GC/MS法测定苹果中2,4-D残留

建立在线GPC-GC/MS技术测定苹果中2,4-D残留的快速检测方法。采用正己烷振荡提取试样中2,4-D,正丁醇-H2SO4溶液衍生化,通过在线GPC-GC/MS系统自动完成从GPC净化、浓缩到GC/MS分析。该方法中2,4-D在实际样品检测中的平均加标回收率为87.9%~99.9%,相对标准偏差(RSD)为2.7%~8.1%。方法的检测限为0.005 mg/kg。     

Reductive dechlorination of 2,4-dichlorophenol using nanoscale Fe~0: influencing factors and possible mechanism

Nanoscale Fe0 was synthesized through a reductive method in this paper. The experiments were per-formed to investigate the reduction of 2,4-dichlorophenol (2,4-DCP) by nanoscale Fe0 under different conditions. The pathways for the reduction of 2,4-DCP by nanoscale Fe0 were discussed. Batch studies demonstrated that the mechanism includes adsorption, dechlorination and cleavage of the benzene ring. Dechlorination, which occurs after 2,4-DCP molecule is adsorbed on the interface of Fe particle, is an interfacial reaction. One or two chlorine atom can be removed from 2,4-DCP to form 2-chlorophenol, 4-chlorophenol or phenol. As the concentration of 2,4-DCP increased, the relative dechlorination ratio decreased. However, the reduced quantities of 2,4-DCP increased. Temperature can influence dechlo-rination rate and pathway. Dechlorination is prior to cleavage of the benzene ring at a higher tempera-ture, but at a lower temperature, adsorption may be the main pathway, and cleavage of the benzene ring may be prior to dechlorination.     

2,4-D/CMC-g-AM/SA/FK微球的制备及其缓释性能

以丙烯酰胺(AM)为单体,制备了羧甲基纤维素钠接枝丙烯酰胺共聚物(CMC-g-AM)。以2,4-二氯苯氧乙酸(2,4-D)为模型药物,以羽毛蛋白(FK)为共混改性剂,采用挤压法制备了CMC-g-AM/海藻酸钠(SA)/羽毛蛋白载药微球。利用红外光谱、光学显微镜、激光粒度仪分别对接枝共聚物的结构、载药微球的形貌以及粒径分布进行了表征,并探讨了不同的接枝共聚物、羽毛蛋白用量、交联剂浓度和交联时间对缓释微球的载药量和缓释性能影响。结果表明,当CMC-g-AM的合成单体比AM:CMC为3:1,羽毛蛋白用量为30%,交联剂浓度为0.7 mol·L-1,交联时间为1 h,载药微球的载药量较高,为16.7%。复合微球平均粒径为1.6 mm。载药微球具有良好的缓释性能,释药曲线符合Higuchi动力学方程。     

Synthesis,characterization and application of dummy-template molecularly imprinted microspheres for 2,4-d butyl ester

Dummy-template molecularly imprinted microspheres were synthesized via precipitation polymerization employing 2,4-D isooctyl ester as the template molecule instead of 2,4-D butyl ester, while methacrylic acid and divinylbenzene were used as functional monomer and cross-linker in acetonitrile or a mixture of acetonitrile and toluene. The microspheres were characterized by scanning electron microscopy, laser particle size analyzer and fourier transform infrared spectrometry. Binding capacity experiment showed that the molecularly imprinted polymers prepared in a mixture of acetonitrile and toluene had a high binding capacity. The performance of microspheres was further assessed by equilibrium binding and kinetic adsorption experiments. The results showed that the apparent maximum adsorption reached up to 1.35 mg·g^?1 within 10 min. Based on the dummy-template microspheres, a molecularly imprinted solid phase extraction-gas chromatography method was developed for the selective analysis of 2,4-D butyl ester in soil samples. The mean recoveries of 2,4-D butyl ester from blank soil samples ranged from 85.9 to 99.3% with relative standard deviations of 4.5–14.3% (n = 5). The limit of detection and the limit of quantification of 2,4-D butyl ester were 0.8 μg·kg^?1 and 2.3 μg·kg^?1, respectively.     

Rapid and simultaneous analysis of dichlorvos, malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid in citrus fruit by flow-injection ion spray ionization tandem mass spectrometry

A simple method for the rapid and simultaneous analysis of dichlorvos (DDVP), malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid (2,4-D) in citrus fruit, which uses flow-injection ion spray ionization tandem mass spectrometry, has been developed for the first time. The method involves the combined use of stable isotopically labeled internal standards (DDVP-d₆, malathion-d₁₀, carbaryl-d₇, and 2,4-D-d₅) and a multiple reaction monitoring technique. The average recoveries for the pesticides at the same concentrations as their tolerance levels (DDVP: 0.1-0.2 μg g⁻¹; malathion: 0.5-4.0 μg g⁻¹; carbaryl: 1.0 μg g⁻¹; 2,4-D: 1.0-2.0 μg g⁻¹) ranged from 90 to 119% with the relative standard deviation (R.S.D.) ranging from 1.0 to 13.1% (n = 5). Analysis time, including sample preparation and determination, was only 15 min. The present method is effective for screening DDVP, malathion, carbaryl, and 2,4-D in citrus fruit.     

Preparation,characterization and heterogeneous catalytic applications of GO/Fe3O4/HPW nanocomposite in chemoselective and green oxidation of alcohols with aqueous H2O2

Graphene oxide ‐ Fe₃O₄ ‐ NH₃⁺H₂PW₁₂O₄₀ ^‐ magnetic nanocomposite (GO/Fe₃O₄/HPW) was prepared by linking amino ‐ functionalized Fe₃O₄ nanoparticles (Fe₃O₄ ‐ NH₂) on the graphene oxide (GO), and then grafting 12 ‐ tungstophosphoric acid (H₃PW₁₂O₄₀) on the graphene oxide ‐ magnetite hybrid (GO ‐ Fe₃O₄ ‐ NH₂). The obtained GO/Fe₃O₄/HPW nanocomposite was well characterized with different techniques such as FT ‐ IR, TEM, SEM, XRD, EDX, TGA ‐ DTA, AGFM, ICP and BET measurements. The used techniques showed that the graphene oxide layers were well prepared and the various stages of preparation of the GO/Fe₃O₄/HPW nanocomposites successfully completed. This new nanocomposite displayed excellent performance as a heterogeneous catalyst in the oxidation of alcohols with H₂O₂. The as ‐ prepared GO/Fe₃O₄/HPW catalyst was more stable and recyclable at least five times without significantly reducing its catalytic activity.     

Spectroscopic,theoretical, and antibacterial approach in the characterization of 5-methyl-5-(3-pyridyl)-2,4-imidazolidenedione ligand and of its platinum and palladium complexes

A series of Pt(IV), Pt(II), and Pd(II) complexes (PtCl₄L₂ (1), PtCl₂L₂ (2), PdCl₂L₂ (3), and Pd₂Cl₄L₂ (4)) with 5-methyl-5-(3-pyridyl)-2,4-imidazolidenedione ligand (L) have been synthesized by the reaction of metal chlorides (K₂[PtCl₆], K₂[PtCl₄], K₂[PdCl₄], and PdCl₂) with L in 1:2 (1-3) and 1:1 (4) molar ratios. The binding manner of L, and the composition and geometry of the metal complexes were examined by elemental analysis, IR, ¹H, and ¹³C NMR spectroscopies. Theoretical calculations invoking geometry optimization of different isomers, performed using density functional theory, suggested that in both gas and solution phases the trans isomers are more stable than the cis ones. The experimental results and calculated molecular parameters, bond distances and angles, revealed slightly distorted octahedral (1) and square-planar (2–4) geometry around the metallic center through the pyridine-type nitrogen (N_py) and chlorine atoms. In 4, the binuclear complex, each palladium atom is coordinated by one nitrogen and three chlorine atoms (one as terminal and two as bridging ligands). Antibacterial activity of L and the corresponding complexes was investigated against six species of microorganisms. Testing was performed by disk diffusion method and minimum inhibitory concentrations (MIC) have been determined. The results showed that the title compounds have the capacity of inhibiting the metabolic growth of bacteria to different extents. In general, the binuclear palladium(II) complex was the most active one.     

纳米Fe/TiO_2粉体的制备及其光催化性能

光催化法是近年来发展较快的一种环境治理技术,掺杂型TiO_2催化剂是当前研究的焦点之一.以四氯化钛为主要原料,利用简单的溶胶法制备了纳米TiO_2、Fe/TiO_2粉体,研究发现掺杂铁,能够有效地延缓锐钛矿型TiO_2向金红石型TiO_2的转变,提高Fe/TiO_2粉体的光催化活性,并且500℃焙烧后的Fe/TiO_2催化剂,在紫外光下催化活性较好.     

铁氧化物/金磁性核壳纳米粒子的制备及其富集与SERS研究

本文用种子生长法制备铁氧化物/金磁性核壳纳米粒子, 并利用SERS对其磁场靶向性进行了检测.     

Two types of carbon nanocomposites: Graphite encapsulated iron nanoparticles and thin carbon nanotubes supported on thick carbon nanotubes, synthesized using PECVD

In this work, graphite encapsulated Fe nanoparticles and thin carbon nanotubes (CNTs) supported on the pristine CNTs, respectively, were synthesized using plasma enhanced chemical vapor deposition via efficiently controlling the flow rate of discharging CH₄ and H₂ gas. The properties of the obtained hybrid materials were characterized with superconducting quantum interference and field emission measurements. The results showed that the encapsulated Fe nanoparticles had diameters ranging from 1 to 30 nm, and this hybrid nanocomposite exhibited a ferromagnetic behavior at room temperature. Thin CNTs with an average diameter of 6 nm were attached to the surface of the prepared CNTs, which exhibited a lower turn-on field and higher emission current density than the pristine CNTs. The Fe nanoparticles either encapsulated with graphite or used as catalyst for thin CNTs growth were all originated from the pyrolysis of ferrocene.     

Preparation and characterization of palladium/polypyrrole-reduced graphene oxide/foamed nickel composite electrode and its electrochemical dechlorination of triclosan

In this study, a new composite electrode of palladium (Pd) nanoparticles dispersed on polypyrrole-reduced graphene oxide (PPy-rGO) loaded on foam-nickel was achieved by galvanostatic method. Characterization of structures, morphology and crystallinity of the synthesized materials were investigated by scanning electron microscopes (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). The results of XPS and XRD demonstrated Pd showed primarily as Pd0. From SEM and TEM results, we had seen that Pd nanoparticles were dispersible well on the composite electrode. Raman spectroscopy was used to show the state of graphene oxide and further demonstrated that PPy and rGO had existed of on the foam Ni matrix. The data of EIS also suggested the charge transfer of the new composite electrode decreased compared to Pd/PPy/foam-Ni and PPy/foam-Ni composite electrodes. The effect of the electropolymerization potential on Pd/PPy-rGO/foam-Ni electrode for removing triclosan (TCS) was examined. It was found that the removal efficiency of TCS on the composite electrode could reach 100% at electropolymerization potential of 0.7 V and reaction time of 100 min.     

Preparation and characterization of Fe_3O_4/Au composite particles

Colloid gold with different sizes has been widely used in immunoassay and nucleic acid detection mainly because of their properties for immobilization of biomolecules, such as antibodies and oligonucleo-tides, through chemical reactions via active group SH on the biomolecules. Magnetic particles modified with various chemical groups on their surface can not only exhibit good magnetic responsiveness to an external magnetic field but also immobilize biomolecules through these chemical groups. As…     

Preparation,characterization, and antibacterial activity of organo-sepiolite/chitosan/silver bionanocomposites

Bionanocomposites with different loadings of silver (Ag) were prepared via synthesis of Ag nanoparticles (AgNPs) using the wet chemical reduction method in the lamellar space layer of the organo-sepiolite/chitosan (O-SEP/CS). The prepared O-SEP/CS/Ag bionanocomposites were characterized using various analysis methods for their structure, morphology, and optical properties. The characteristic absorption bands from the UV–visible absorption spectrum confirmed the formation of AgNPs. The antibacterial activities of O-SEP/CS/Ag bionanocomposites were investigated against gram-positive and gram-negative bacteria using the disc diffusion method. The results suggest that O-SEP/CS/Ag bionanocomposites can be useful in wide range of bio-medical applications because of high antibacterial activity.     

Fe-Ni/TiO2纳米管阵列电极的制备、表征及光电催化还原五氯酚活性

采用阳极氧化法和浸渍电沉积联用法制备了不同负载量的Fe-Ni/TiO2纳米管阵列电极. 通过扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)和电化学测量等手段对样品的微观形貌、 晶体结构和光电响应等特性进行分析. 考察了在0.6 V偏压下, 所制备的电极对五氯酚的光电催化还原性能. 结果表明, 适量的Fe和Ni纳米颗粒的负载, 降低了TiO2纳米管阵列光生电子-空穴对的复合几率; 浸渍电沉积5次的Fe-Ni/TiO2纳米管阵列电极光电催化还原降解五氯酚的效率为91.35%, 明显高于TiO2纳米管阵列电极.