Dechlorination of carbon tetrachloride by Nanoscale Nickeled Zero‐Valent Iron @ Multi‐Walled Carbon Nanotubes: Impact of reaction conditions,kinetics and mechanism

The nanoscale nickeled zero‐valent iron @ multi‐walled carbon nanotubes (NF@MWCNTs) were synthesized, characterized and used to dispose carbon tetrachloride (CT) in aqueous solution. Scanning electron microscopy (SEM), X‐ray energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) and Brunauer–Emmett–Teller (BET) gas sorptometry measurements were conducted to characterize the microstructure of the NF@MWCNTs. And batch experiments under different operation parameters were conducted to investigated the activity of NF@MWCNTs on degrading CT, including the content of NF@MWCNTs composites, temperature, catalyst dosage, initial pH and different anions. The experimental results showed that 4% nickel content of Ni/Fe bimetal and 2:1 doping ratio of Fe/MWCNTs were the wise choices in this study, which provided excellent degradation efficiency of CT when compared with nanoscale zero‐valent iron (nZVI) (97.44% and 55.28%, respectively). That was benefited from the fact that MWCNTs as an excellent support material could reduce the activation energy of 7.952 kJ/mol, and the nickel metal further reduced the reaction activation energy of 11.022 kJ/mol as presented in the conceptual model. Beyond that, NF@MWCNTs showed good reusability after five times consecutive reaction. Based on these, the reaction mechanism and degradation pathway also had been discussed.     

Rapid reductive degradation of dye contaminated water by using a core-shell nano zerovalent iron (nZVI)

We report on the synthesis of zero valent iron nano particles (nZVI) via chemical reduction method. The large peak visible in the XRD pattern reveals the presence of an amorphous phase of iron. SEM and TEM images signify the dendritic morphology and core-shell-like structure of manufactured nZVI particles respectively. Methylene blue dye (MB) was used as model contaminant to assess the reductive degradation proficiency of nZVI. With complete elimination of MB, the fresh synthesized nZVI exhibited the best performance (97%), while the regenerated nZVI had an 85.1% MB removal efficiency after five regenerations. The equilibrium data of adsorption were fitted to eight different kinetic and isothermal models. The effects of critical operating factors such as pH, varied amounts of nZVI and dye concentration, adsorption temperature, and adsorption time were also studied. A presumptive reaction mechanism and function of core-shell construction in contaminant sequestration has also been investigated.     

Optimizing the degradation of dichlorvos in aqueous solution using nZVI DTPA+H2O2 and its detection using ac conductivity measurement with the help of response surface methodology

Degradation of organic pollutants in wastewater is a common subject of discussion under advanced oxidation process. To detect the degradation of colourless organic pollutants conventional analytical techniques are available but their sophistication makes it difficult to pursue in all form of chemical laboratories. In the present study it was found that during degradation of Dichlorvos using diethylene triamine pent acetic acid (DTPA) stabilized nano zero valent iron (nZVI), COD removal and ac conductivity change has been done simultaneously. In this degradation study the heterogeneous Fenton type oxidation method was employed and an LCR circuit (which contains inductor, capacitor and resistor) was used to measure the ac conductivity. This study aims to find out a correlation between ac conductivity and COD removal using simple response surface methodology (RSM) so that the degradation of colourless pollutants can be estimated easily and also to identify the best processing parameters to optimise Dichlorvos degradation. It was found that COD removal in most of all cases, was more than 60% when the change in final ac conductivity more than 600% with respect to initial value. All of the experimental results were in good accord with the projected outcome.     

Synthesis of nanoscale zero‐valent iron modified graphene oxide nanosheets and its application for removing tetracycline antibiotic: Response surface methodology

Nowadays, pharmaceutical antibiotics are known as a serious class of pollutants. Therefore, it is important to develop effective methods for removing these pollutants from aqueous media. Different methods were applied for this purpose, and among these methods, chemical reduction by a cheap and eco‐friendly nanocatalyst is the most efficient and simplest method. In this research, based on graphene oxide supported by zero‐valent iron in mono‐, bi‐, and tri‐metallic systems, various nanocomposites were synthesized and used to degrade tetracycline as a model antibiotic from aqueous media. An investigation was carried out on the synergic effect among graphene oxide and the nano zero‐valent iron‐based tri‐metallic system as well as removal efficiencies. It was found that higher degradation efficiency is yielded by graphene oxide supported by Fe/Cu/Ag tri‐metallic system. The maximum synergic effect occurs at an acidic medium. The Brunauer–Emmett–Teller, Fourier transform spectroscopy, scanning electron microscopy‐energy dispersive X‐ray analysis, transmission electron microscopy, and X‐ray diffraction analysis were used to characterize the synthesized nanocomposites, which has successfully proved the loading of nanoscale Fe/Cu/Ag tri‐metallic on a graphene oxide support. The central composite design was used to model and optimize all involved variables affecting antibiotic removal efficiency. The consequences illustrated the optimum condition regarding the removal of 50 ppm of tetracycline, for the nanocomposites dose of 3.0 mg ml^?1, the contact time of 30 min, and pH of 2, was achieved using the simplex non‐linear optimization method. Moreover, antibiotic adsorption kinetic models were also investigated. Finally, the tetracycline removal from aqueous media at different concentrations, 25, 50, and 75 ppm, was successful by applying the proposed nanocomposite, and the results showed tetracycline removal efficiencies of above 70%.     

零价铁耦合厌氧微生物法在废水处理中的应用

零价铁(ZVI)与厌氧微生物的耦合是一项很有前景的技术,在难降解有机废水的去除中得到了广泛关注。该耦合技术将ZVI技术的高效性与厌氧生物技术的经济性有效融合,在多元微电场和厌氧微生物协同作用下,有效降低难降解有机物的生物抑制性和毒性。本文综述了此技术处理工业废水的潜在机理、实际应用中主要操作参数及影响条件以及处理含氯化合物、重金属、染料等生物难降解污染物的研究进展。归纳了ZVI与厌氧微生物耦合对上述污染物进行高效去除的研究现状,并对该技术在实际工程应用方面的可行策略进行了展望。     

Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron

Zero-valent iron (ZVI) nanoparticles tend to agglomerate, resulting in a significant loss in reactivity. To address this issue, synthesized bentonite-supported nanoscale zero-valent iron (B-nZVI) was used to remove azo dye methyl orange (MO) in aqueous solution. Batch experiments show that various parameters, such as pH, initial concentration of MO, dosage, and temperature, were affected by the removal of MO. Scanning electron microscopy (SEM) confirmed that B-nZVI increased their reactivity and a decrease occurred in the aggregation of iron nanoparticles for the presence of bentonite (B). Using B-nZVI, 79.46% of MO was removed, whereas only 40.03% when using nZVI after reacting for 10 min with an initial MO concentration of 100 mg/L (pH=6.5). Furthermore, after B-nZVI reacted to MO, XRD indicated that iron oxides were formed. FTIR showed that no new bands appeared, and UV-vis demonstrated that the absorption peak of MO was degraded. Kinetics studies showed that the degradation of MO fitted well to the pseudo first-order model. A degradation mechanism is proposed, including the following: oxidation of iron, adsorption of MO to B-nZVI, formation of Fe(II)-dye complex, and cleavage of azo bond. Finally, the removal rate of MO from actual wastewater was 99.75% when utilizing B-nZVI.     

铋铁复合氧化物光催化材料的制备及其性能研究

采用共沉淀法制备了一系列铋铁复合氧化物光催化剂,并以可见光降解甲基橙为模型反应,研究其在可见光照射下降解甲基橙的光催化性能。详细考察了p H值、铋铁摩尔比、煅烧温度等对其光催化性能的影响。在优化条件下,铋铁摩尔比为2∶1、p H=3~4时制备出的样品具有较好的光催化性能,甲基橙的降解率可达到91.95%。     

Rapid decolorization of water soluble azo-dyes by nanosized zero-valent iron immobilized on the exchange resin

Nanosized zero-valent iron (NZVI) supported on the cation exchange resin was synthesized and applied to decompose some water soluble azo dyes. The decomposition efficiency for azo dyes was evaluated by using the aqueous suspensions and parked column of this material. Batch experiments indicated that this novel material exhibited excellent degradation ability for 0.05 g·L1 of Acid Orange 7, Acid Orange 8, Acid Orange 10, Sunset Yellow, and Methyl Orange, with decolorization ratio up to 95% in 4 min; pH value was the key factor for degradation and H was one of the reactants; adsorption of azo dyes onto the material existed at the beginning but reduced gradually until disappearing completely. For the packed column system, 58%~90% of azo dyes were decomposed in the 1st circle of solution passing through the column, and the adsorption onto the materials could accelerate the degradation azo dyes with the increasing reaction time. During the degradation process, Fe2 , the product of NZVI, was exchanged to the resin again and could be reduced to Fe0 by KBH4 for reusing. The 10th refreshed NZVI possessed reductive activity up to 90% of the newly systhesized NZVI. Decomposing pollutants in the aqueous solution with columns packed with NZVI immobilized on the cation exchange resin is a promising technology that can solve the reclaiming and refreshing problem of NZVI.     

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.     

纤维负载炭黑金属酞菁轴向配合物仿酶高效催化降解水体中有机污染物

天然血红素基过氧化氢酶具有高选择催化性, 但易失活变性. 为提高其活性和稳定性, 以性能稳定的十六氯铁酞菁(FePcCl₁₆)为活性中心, 四氨基吡啶为配体, 炭黑(CB)为载体, 合成了仿酶催化剂炭黑十六氯铁酞菁轴向配合物(FePcCl₁₆-Py-CB); 通过热黏合法将其负载于低熔点皮芯聚酯纤维(LMPET)上, 生成易与水体分离的纤维负载型仿酶催化剂FePcCl₁₆-Py-CB@LMPET, 并以H₂O₂为氧化剂, 地赛米松(DXMS)为底物, 构筑仿酶催化体系. 研究了该催化体系在温和条件下的催化性能及循环使用性能, 探讨了催化体系的催化机理及DXMS的降解历程. 结果表明, 异裂H₂O₂产生的高价铁氧[Fe(Ⅳ)=O]为催化体系中的主要活性物种, 体系呈现出优异的催化性能和稳定性能. 该催化体系在120 min内降解的最终产物均为小分子酸.     

Nanoscale Zero‐Valent Iron Particles Supported on Reduced Graphene Oxides by Using a Plasma Technique and Their Application for Removal of Heavy‐Metal Ions

Nanoscale zero‐valent iron particles supported on reduced graphene oxides (NZVI/rGOs) from spent graphene oxide (GO)‐bound iron ions were developed by using a hydrogen/argon plasma reduction method to improve the reactivity and stability of NZVI. The NZVI/rGOs exhibited excellent water treatment performance with excellent removal capacities of 187.16 and 396.37 mg g^?1 for chromium and lead, respectively. Moreover, the NZVI/rGOs could be regenerated by plasma treatment and maintained high removal ability after four cycles. X‐ray photoelectron spectroscopy analysis results implied that the removal mechanisms could be attributed to adsorption/precipitation, reduction, or both. Such multiple removal mechanisms by the NZVI/rGOs were attributed to the reduction ability of the NZVI particles and the role of dispersing and stabilizing abilities of the rGOs. The results indicated that the NZVI/rGOs prepared by a hydrogen/argon plasma reduction method might be an effective composite for heavy‐metal‐ion removal.     

Removal of Chromium(VI) from Groundwater Using Oil Shale Ash Supported Nanoscaled Zero-valent Iron

Oil shale ash(OSA) supported nanoscaled zero-valent iron(OSA-nZVI) was used as a rapid and efficient reductant for Cr(VI) reduction. The optimal mass ratio of nZVI to OSA and the optimal dosage were explored. The effects of initial pH, reaction temperature, initial Cr(VI) concentration, and common cations and anions in groundwater on Cr(VI) reduction were determined in batch experiments. The results show that the optimum initial pH is 5.0. The reaction temperature has a positive effect on Cr(VI) reduction while the real groundwater has a negative effect. Additionally, 84.22% Cr(VI) was still reduced by 3 g/L OSA-nZVI(1:2)(mass ratio of OSA to Fe⁰ was 1:2) within 120 min for 50 mg/L Cr(VI) under conditions of 10℃ and unadjusted pH.     

镀铜铁屑-H_2O_2催化氧化降解含酚废水

采用镀铜铁屑代替传统Fenton体系中的FeSO4作为催化剂,通过改变H2O2与镀铜铁屑的投加量、溶液的pH值、反应温度、反应时间等条件,研究了该体系对处理苯酚废水的影响。结果表明,常温下处理实际含酚印染废水,在pH值为4~6,30%H2O2 12mL/L,镀铜铁屑5g/L,反应时间为45min时,COD去除率可达96%,其CODCr从5827mg/L降至419mg/L,色度从2000降至30,符合国家三级排放标准。     

The capacity and mechanisms of various oxidants on regulating the redox function of ZVI

It is well known that zero-valent iron(ZVI) could catalyze the oxidation of various oxidants to realize the rapid oxidation removal of pollutants. However, in this study, we found that the addition of different oxidants could regulate the redox function of ZVI system. In three different co-treatment systems, the effects of different oxidizers(peroxymonosulfate(PMS), persulfate(PDS), hydrogen peroxide(H_2O_2))dosages on the ratios of oxidative degradation rate and reductive degradation rate of p-nitrophenol(PNP)were studied. The effect of the H~+ released from oxidizers and the generated reactive oxygen species(ROS) in ZVI/PMS, ZVI/PDS, ZVI/H_2O_2 systems were detailed discussed. Especially, the contribution of generated ROS for reductive degradation of PNP was quantified in the ZVI/H_2O_2 system. Based on the results of TOC removal, UV–vis absorption spectra, and intermediates concentration curves, it was found that the degradation of PNP changed from reduction to oxidation with the increase of oxidant proportion.When the molar ratio of ZVI to oxidizer equal to 100, PNP was mainly degraded by reduction accompanied by slight oxidation. Combined with the results of SEM-EDS and XPS, it was confirmed that the enhanced degradation of PNP under the addition of oxidant was mainly related to the generated ROS,the additional H~+, and the corrosion products of ZVI.     

Zero‐Valent Aluminum as Reducer in Sodium Carbonate Solution for Degradation of Imidacloprid

Imidacloprid (IMI ) was reduced by zero‐valent aluminum (ZVAl ) in sodium carbonate solution and tested by high‐performance liquid chromatography (HPLC ). The IMI degradation rate was heavily dependent on Na₂CO₃ concentration and reaction time but only slightly on temperature, reaching 99.4% in 0.5 mol/L Na₂CO₃ solution with 5 g/L ZVAl in 60 min. The degradation of IMI follows first‐order kinetics. We used high‐performance liquid chromatography‐mass spectrometry (HPLC‐MS ) for analyzing the transformation products, and found that IMI disintegrated into IMI urea, IMI guanidine, IMI nitrosamine, and 1‐choloro‐5‐methcyclohea‐1,4‐diene.     

壳聚糖稳定纳米铁的制备及其对地表水中Cr(Ⅵ)的去除性能

以可生物降解材料壳聚糖为稳定剂, 制备了平均粒径为 82.4 nm的纳米零价铁颗粒. 热重分析表明, 经壳聚糖改性后, 纳米铁在340 ℃以下具有很好的热稳定性. 批试验结果表明, 壳聚糖稳定纳米铁对水体中Cr(Ⅵ)有很强的去除能力, 在空气中放置60 d后, 壳聚糖稳定纳米铁仍具有较高的活性. 壳聚糖分子中的氨基和羟基可与Fe(Ⅲ)形成稳定的螯合物, 阻止Cr(Ⅲ)和Fe(Ⅲ)共沉淀的形成, 从而促进零价铁的腐蚀和Cr(Ⅵ)的还原去除.     

Evaluation of mutual connections between zero-valent iron reactivity and groundwater composition in trichloroethylene degradation

Zero-valent iron Permeable Reactive Barriers (PRBs) are an efficient and relatively low cost in situ technology for the remediation of aquifers polluted by chlorinated solvents. The groundwater composition and the zero-valent iron reactive material are linked by mutual connections. The groundwater, to a certain extent depending on its composition, is able to oxidize the metallic iron, thus decreasing its reactivity; on the other hand, the dechlorination process and the leaching of chemical species from the reactive substrate may deeply modify groundwater composition. In this study the results of some batch and leaching column tests, performed by means of Connelly iron (Environmental Technologies Inc., Canada) and different aqueous phases (distilled water and an artificial groundwater) are compared, to evaluate the influence of groundwater composition on the reactivity of the iron material for trichloroethylene (TCE) remediation. The degradation mechanisms of the pollutant are discussed. On the grounds of the gathered results the aqueous phase composition shows a strong influence on TCE degradation kinetics obtained by means of Connelly iron; in fact the presence of dissolved substances accelerates TCE degradation.     

Zero‐valent Iron Nanoparticles Modified Screen‐printed Electrode for FIA or HPLC Amperometric Detection of Metronidazole in Pharmaceutical Formulations

A zero‐valent iron nanoparticles modified electrode was employed as an amperometric detector in flow conditions to determine metronidazole and 2‐methyl‐5‐nitroimidazole in pharmaceutical formulations. Flow injection analysis at ?0.6 V (vs. Ag) achieved limits of detection of 2 and 6 μM for metronidazole and 2‐methyl‐5‐nitroimidazole, respectively, but the analysis was not discriminative between the two compounds. When reverse phase high performance liquid chromatography was applied previous to the electrochemical detection both analytes could be analysed simultaneously. However, the limits of detection slightly increased (10 μM) as a consequence of the use of an organic solvent and a lower sample volume. The relative standard deviation of analytical repeatability was <4.0 % in both techniques. The methods were validated by comparing the results obtained from the analysis of commercial samples with those provided by HPLC‐DAD and no significant differences were detected. Results probed that the modified electrode was a successful tool in the FIA and HPLC analysis of nitro compounds.     

纳米铁粉降解水中三硝基甲苯的条件优化与降解机理

研究了纳米铁粉降解水中三硝基甲苯(TNT)的影响因素;利用傅立叶变换红外光谱和紫外光谱分析了其降解机理.结果表明:将初始浓度为80.0mg/L、pH为4.00的TNT水溶液与5.0g/L的纳米铁粉在转速200r/min、温度40℃的振荡器中反应3h,水中TNT的浓度可降至0.1mg/L以下,降解率达到99%以上;就TNT的降解机理而言,其降解过程是纳米铁粉给出电子被氧化、TNT分子中的硝基接受电子被还原的过程.     

Formation of High‐Valent Iron–Oxo Species in Superoxide Reductase: Characterization by Resonance Raman Spectroscopy

Superoxide reductase (SOR), a non‐heme mononuclear iron protein that is involved in superoxide detoxification in microorganisms, can be used as an unprecedented model to study the mechanisms of O₂ activation and of the formation of high‐valent iron–oxo species in metalloenzymes. By using resonance Raman spectroscopy, it was shown that the mutation of two residues in the second coordination sphere of the SOR iron active site, K₄₈ and I₁₁₈, led to the formation of a high‐valent iron–oxo species when the mutant proteins were reacted with H₂O₂. These data demonstrate that these residues in the second coordination sphere tightly control the evolution and the cleavage of the O? O bond of the ferric iron hydroperoxide intermediate that is formed in the SOR active site.