地下水修复中纳米零价铁材料制备及应用综述

纳米零价铁（nZVI）具有较强的还原和吸附能力,能有效去除多种类型的污染物质,在地下水环境修复领域一直备受关注。但由于其易团聚和易钝化等缺陷,在实际应用过程中还存在着许多问题。本文综述了nZVI的常用制备方法,并对nZVI的常用改性方法进行归纳,分析各种改性方法起到的具体作用,指出改性过后的复合材料依然存在着的问题。在此基础上,阐述了改性nZVI在去除地下水中有机污染物和无机污染物的应用进展,总结了改性nZVI材料在去除过程中起到的具体作用和反应机制,并进一步归纳现阶段nZVI在地下水修复中的传输手段。根据已有研究成果,指出应改进现有制备方法实现nZVI的量产,在考虑nZVI生物毒性和材料再回收的前提下,合理使用多种改性方式实现nZVI的材料制备,选择符合污染场地实际情况的传输手段,从而提高nZVI在地下水污染修复中的使用寿命和对目标污染物的处理效果。     

Synthesis of clay-supported nanoscale zero-valent iron using green tea extract for the removal of phosphorus from aqueous solutions

This study addresses the synthesis of nanoscale zero-valent iron (nZVI) in the presence of natural bentonite (B-nZVI) using green tea extract.The natural bentonite and B-nZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations,pH levels and contact time.The desorption of phosphorus (P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method.The characterization of FTIR,SEM,and XRD indicated that nZVI was successfully loaded to the surface of natural bentonite.The sorption of phosphorus on B-nZVI was observed to be pH-dependent,with maximum phosphorus removal occurring at the pH range of 2 to 5.The results demonstrate that the maximum sorption capacities of natural bentonite and B-nZVI were 4.61 and 27.63 mg·g-1,respectively.Langmuir,Freundlich,and Redlich-Peterson models properly described the sorption isotherm data.For either adsorbent,desorption isotherms did not coincide with their corresponding sorption isotherms,suggesting the occurrence of irreversibility and hysteresis.The average percentages of retained phosphorus released from natural bentonite and B-nZVI were 80％ and 9％,respectively.The results indicated that sorption kinetics was best described by the pseudo-second-order model.The present study suggests that B-nZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.     

Eco friendly adsorbents for removal of phenol from aqueous solution employing nanoparticle zero-valent iron synthesized from modified green tea bio-waste and supported on silty clay

The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI) utilizing an aqueous extract of green tea waste as a reductant with ferric chloride. Also, the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI). The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR), scanning electron microscope(SEM), X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET), and zeta potential(ζ). The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis, with silty clay an adequate support. Additionally, the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI. To determine the optimum conditions, the impact of diverse experimental factors(i.e., initial pH, adsorbent dose, temperature, and concentration of phenol) was studied. Langmuir, Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium. The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model. The appropriateness of pseudo_first_order and pseudo_second_order kinetics was investigated. The experimental kinetics data were good explained by the second-order model. The thermodynamic parameters(ΔH0, ΔS0, andΔG0) for NZVI and SC-NZVI were determined. The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI, were found to be 94.8% and 90.1%, respectively.     

Selective Separation of Nickel (II) and Cobalt (II) from Waste Water by Using Continuous Cross-Flow Micellar Enhanced Ultrafiltration with Addition of Chelating Agent

The performance of continuous cross-flow micellar enhanced ultrafiltration (MEUF) is evaluated for the selective separation of nickel (Ni²⁺) and cobalt (Co²⁺) from the aqueous stream using anionic surfactant sodiumdodecyl sulfate (SDS) and the mixture of the anionic and nonionic surfactant (SDS+TritonX-100) with the addition of iminodiacetic acid (IDA) as a chelating agent. Operating parameters like operating time (upto 100 min), cross flow rate (100–175 mL/min.), pH of the feed solution (3-6 Cheryan , M. ( 1998 ) Process Design in Ultrafiltration and Microfiltration Handbook ; Technomic Publishing Co. Inc : USA . Scamehorn , J.F. ; Ellington , R.T. ; Christian , S.D. ; Penny , B.W. ; Dunn , R.O. ; Bhat , S.N. ( 1986 ) Removal of multivalent metal cations from water using micellar-enhanced ultrafiltration . AIChE Symp. Ser. , 82 ( 250 ): 48 – 58 . Baek , K. ; Yang , J.W. ( 2004 ) Cross flow micellar-enhanced ultrafiltration for removal of nitrate and chromate: competitive binding . J. Hazard. Mater. , B108 : 119 – 123 . Yurlova , L. ; Kryvoruchko , A. ; Kornilovich , B. ( 2002 ) Removal of Ni (II) ions from waste- water by micellar-enhanced ultrafiltration . Desal. , 144 : 255 – 260 . ), molar concentration ratio of the chelating agent to metals (C/M ratio, 0.5–2.5), and molar concentration ratio of the surfactant to metals (S/M ratio, 5–9) were studied to investigate the effectiveness of the process on selective separation. For the single surfactant system at all empirically selected parameters, 92% Ni²⁺ in the permeate and 94% Co²⁺ in the retentate was achieved whereas for the mixed surfactant system 93% Ni²⁺ in permeate and 84% Co²⁺ in retentate was achieved. Flux variation for single and mixed surfactant system was studied. Flux observed for the single surfactant system was 36 L/m².h and for the mixed surfactant system was 31.5 L/m².h. Flux measurement also indicates insignificant fouling of the membrane.     

零价铁还原催化臭氧氧化靛蓝二磺酸钠的研究

建立了零价铁还原催化臭氧氧化靛蓝二磺酸钠的体系,通过一级动力学分析分别考察了零价铁粒径、底物初始浓度、零价铁的投加量、pH、温度以及废水中常见的阴离子(Cl~-、NO_3~-、SO_4~(2-))等条件对反应速率的影响。通过自由基抑制试验与电子自旋共振法(ESR)以及离子阱质谱等实验分析来进一步探讨零价铁还原催化臭氧氧化体系的反应机理。     

The role of Ni2+ diffusion on the reducibility of NiO/MgO system: A combined TRP-XPS study

The progressive dissolution of nickel ions in the lattice of MgO matrix, promoted by the calcination temperature, has been monitored using XPS. The reducibility of Ni/MgO catalysts is affected by the modification of the surface chemical composition. TPR peaks have been correlated with several NiO forms. Both XPS and TPR results indicate a different behaviour pattern for the supported and physically mixed NiO/MgO systems, and this has been attributed to the different available contact area between NiO and MgO. The formation of both NiO rich and MgO rich NiO-MgO solid solutions, with the tendency to evolve towards the bulk solid solution, has been invoked to explain the substantial changes in the TPR pattern of the different air calcined systems.     

零价铁处理污水的最新研究进展

零价铁以其低毒、廉价、易操作而且对环境不会产生二次污染等优点,而在水污染治理中受到重视。作者介绍了零价铁处理污水的机理并综述了其处理包括重金属废水、偶氮染料废水、氯代有机物废水、硝基芳香族化合物废水、硝酸盐废水等在内各种废水的最新研究进展。指出了零价铁废水处理技术的研究方向,包括对纳米级零价铁的研究、对零价铁去除污染物的机理研究及零价铁与其他技术联用的研究。     

氯酚类有机物在超声波／零价铁体系中降解特性的研究

以2-氯酚、2,4-二氯酚、2,4,5-三氯酚、2,3,4,6-四氯酚及五氯酚等氯酚类化合物（CPs）为目标污染物,研究了CPs在超声波／零价铁联合体系中（US／Fe^0）的降解特性。结果表明,在同一条件下,苯环上的氯取代基越多,降解速率越大;当氯原子取代得越多,碳正离子的形成速度越快,反应活性越大;随着氯取代基增多,分子的（Elumo－Ehomo）^2减小,该分子越不稳定。     

Solvent-Free Preparation of Tannic Acid Carbon Dots for Selective Detection of Ni2+ in the Environment

Carbon dots (CDs) are widely used nanomaterials that not only exhibit good biocompatibility and photostability, but also benefit from a simple preparation process and easy functionalization, making them promising for broad applications in the fields of heavy metal ion detection and optoelectronic devices. Based on the excellent optical properties of CDs and the current situation of increasing energy shortages, this paper selects the natural polyphenolic compound tannic acid (TA) found in biomass materials as the carbon source and innovatively adopts a simple and convenient solvent-free pyrolysis method without auxiliary reagents or solvents. The CDs with good water solubility and certain fluorescence properties were directly prepared under the condition of high temperature, and the obtained CDs exhibited blue fluorescence, and a high QY of 35.4% was obtained at 300 °C. The analysis and results demonstrate the selectivity of these CDs for the detection of various metal ion solutions. In particular, these CDs are sensitive to Ni²⁺ and can be used as fluorescent sensors for the efficient and sustainable detection of Ni²⁺, whereas previous sensors were often specific to Fe³⁺ and Hg²⁺. Thus, a new sensing technique has been developed for the detection of Ni²⁺ to achieve more sensitive and rapid detection.     

零价铁活化过硫酸钠降解苯酚的研究

采用零价铁活化过硫酸钠的方式产生具有强氧化性的硫酸根自由基,以苯酚为目标污染物,考察了硫酸根自由基对苯酚的氧化降解行为。系统研究了零价铁投加量、过硫酸钠的投加量、不同温度、恒温震荡的时间、苯酚浓度、p H值对降解苯酚的影响。实验结果表明：在反应温度为35℃、p H为3、过硫酸钠用量为0.07g、零价铁用量为0.07g、苯酚浓度为10mg/L的条件下,恒温时间为90min时苯酚的降解情况最好,其降解率可以达到90.1%。     

Olive leaves extract mediated zero-valent iron nanoparticles: synthesis,characterization, and assessment as adsorbent for nickel (II) ions in aqueous medium

Abstract

Zero-valent iron nanoparticles (NZVI-NPs) possess significantly high surface area and volume ratio, and this unique surface characteristic has enhanced reactivity to their adsorption potential. In this work, a bio-matter (Olive leaves extract) is deployed as a nature-inspired reducing agent for the synthesis of NZVI-NPs. The particle size of NZVI-NPs has been determined using particle sizer. The NZVI-NPs are characterized using analytical and morphological techniques such as ultraviolet???visible spectroscopy (UV???vis), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), and Fourier transform infrared (FTIR) spectroscopy. The average crystalline size of NZVI-NPs are around 30–60?nm while maximum adsorption is at 225?nm. XRD spectrum shows two distinctive diffraction peaks at 25.40° and 42.50° corresponding to lattice plane value indexed at (200) and (222) planes of faced centered cubic (FCC). At optimized experimental conditions, NZVI-NPs show 97% removal efficiency of Ni⁺² ions from aqueous solution. The equilibrium time has been found to be 55?min and the monolayer maximum adsorption capacity is 139.5?mg/g. Kinetically, Ni⁺² ions adsorption has been modelled using various physical isotherms and the data best fitted Freundlich isotherm model and pseudo-first-order kinetic; revealing a maximum adsorption capacity of 139.5?mg/g at 25?±?3?°C and pH of 6.5. Desorption tests affirm the possibility of recovering reasonable amount of NZVI-NPs after used. The specific surface area of the NZVI-NPs sample measured by BET analysis is 21.9967 m²/g indicating a high adsorption capacity.     

Tunable synthesis of SiO2-encapsulated zero-valent iron nanoparticles for degradation of organic dyes

A series of nanocomposites consisting of zero-valent iron nanoparticles (ZVI NPs) encapsulated in SiO₂ microspheres were successfully synthesized through a successive two-step method, i.e., the wet chemical reduction by borohydride followed by a modified Stöber method. The as-synthesized nanocomposites were characterized using X-ray diffraction, field emission scanning electron microscopy, vibrating sample magnetometer, and inductively coupled plasma-atomic emission spectrometer. The catalytic performance of SiO₂-encapsulated ZVI nanocomposites for the degradation of organic dyes was investigated using methylene blue (MB) as the model dye in the presence of H₂O₂. The results showed that the degradation efficiency and apparent rate constant of the degradation reaction were significantly enhanced with increased ZVI NPs encapsulated in SiO₂ microspheres, whereas the dosage of H₂O₂ remarkably promoted degradation rate without affecting degradation efficiency. The content-dependent magnetic property ensured the excellent magnetic separation of degradation products under an external magnet. This strategy for the synthesis of SiO₂-encapsulated ZVI NPs nanocomposites was low cost and easy to scale-up for industrial production, thereby enabling promising applications in environmental remediation.     

颗粒活性炭载纳米零价铁去除水中的Cr(Ⅵ)

以Fe2+溶液为原料、NaBH4为还原剂,采用传统液相还原技术合成了颗粒活性炭(GAC)载纳米零价铁(nZVI)复合材料GAC-nZVI,用扫描电镜对GAC-nZVI进行表征,通过间歇实验考察了其对去除Cr(VI)的影响。结果表明,GAC能阻止nZVI颗粒聚集,合成的GAC-nZVI能有效去除水中的Cr(VI)。在Cr(VI)初始浓度50 mg/L、温度40℃和pH=2.0、投加GAC-nZVI 3.0 g/L的条件下反应5 min,Cr(VI)去除率为99.4%。pH=2.0?4.0时,处理后水中总铬浓度均低于1 mg/L,表明残留少量Cr(III)。随pH值和Cr(VI)浓度增加,Cr(VI)去除率降低;随反应温度和GAC-nZVI投加量增加,Cr(VI)去除率增加。准一级动力学模型可用于描述Cr(VI)的去除过程。相同条件下,GAC-nZVI去除Cr(VI)的反应速率常数达0.19797 min?1,为原颗粒活性炭反应速率常数0.0023 min?1的86倍。随pH值降低或反应温度和GAC-nZVI投加量增加,反应速率常数增加。     

Wool powders used as sorbents to remove Co ions from aqueous solution

The Co²⁺ sorption of two wool powders was investigated using its radioisotope ⁵⁷Co (T_1/2 = 271.8 days and γ = 122.1 and 136.5 keV) as a tracer. The effects of the type of buffer, the pH value, the contact time and the initial concentration of Co²⁺ on the sorption behaviour of wool powders were studied. The Co²⁺ releasing ability of wool powders and the re-use of wool powders to sorb Co²⁺ were also examined. The optimum sorption of Co²⁺ by the powders occurred at pH 8 in phosphate buffer and pH 10 in ammonium sulphate buffer. Fourier-transform infrared spectroscopy (FTIR) was used to study the changes in chemical structure of the wool after exposure to both buffer solutions. Compared to the untreated wool fibre, the fine wool powders showed rapid sorption rates and high sorption capacities for Co²⁺. Co²⁺ ions were recovered after exposing the Co²⁺ loaded wool to HCl (0.1 M) and buffer at pH 3 (glycine/sodium chloride). After releasing Co²⁺ ions from wool powders, the efficiency of wool powders re-used to sorb Co²⁺ was 80% of that of the fresh wool powders. It is concluded from this study that wool powder can be used as an efficient sorbent to remove and release Co²⁺ from solution.     

Adsorption and desorption of Ni on Na-montmorillonite: Effect of pH, ionic strength, fulvic acid, humic acid and addition sequences

Humic substances and clay minerals have been studied intensively because of their strong complexation and adsorption capacities. In this work, adsorption of Ni²⁺ on Na-montmorillonite was studied using batch technique under ambient conditions. Effect of pH, ionic strength, solid content, humic acid (HA), fulvic acid (FA) and the addition sequences of fulvic acid/Ni²⁺/montmorillonite on Ni²⁺ adsorption was also investigated. The results indicate that adsorption of Ni²⁺ on montmorillonite are strongly dependent on pH and ionic strength. The adsorption of Ni²⁺ is mainly dominated by surface complexation and ion exchange. The adsorption–desorption hysteresis suggests that the adsorption of Ni²⁺ is irreversible. The thermodynamic parameters (ΔH, ΔS, and ΔG) are calculated from the temperature dependence, and the results suggest that the adsorption reaction is endothermic and spontaneous. The presence of FA and the addition sequences of FA/Ni²⁺/montmorillonite do not influence the adsorption of Ni²⁺ on FA bound montmorillonite hybrids. Montmorillonite is a suitable candidate for pre-concentration and solidification of Ni²⁺ from large volume of solutions.     

氯苯类有机物在超声波/零价铁体系中降解特性的研究

以氯苯、邻二氯苯、间二氯苯、对二氯苯、1,2,4-三氯苯等氯苯类化合物(CBs)为目标污染物,研究了CBs在超声波/零价铁联合体系中(US/Fe0)的降解特性。结果表明,用超声波协同零价铁降解氯苯类有机物具有很好的去除效果,在同一条件下,降解速率常数依次为:K1,2,4-TCB>Ko-DCB>Km-DCB>Kp-DCB>KCB,即苯环上的氯取代基越多,降解越容易,氯苯类有机物的反应属于准一级反应。     

Characterization of electrochemiluminescence of tris(2,2′-bipyridine)ruthenium(II) with glyphosate as coreactant in aqueous solution

Glyphosate, a phosphorus-containing amino acid type herbicide was used as a coreactant for studying of electrochemiluminescence (ECL) reaction of tris(2,2′-bipyridyl)ruthenium(II) [Ru(bpy)₃²⁺] in an aqueous solution. In a phosphate buffer solution of pH 8, glyphosate itself was known to be electrochemically inactive at glassy carbon electrode, however, it participated in a homogeneous chemical reaction with the electrogenerated Ru(bpy)₃³⁺, and resulted in producing Ru(bpy)₃²⁺ species at the electrode surface. Kinetic and mechanistic information for the catalysis of glyphosate oxidation were evaluated by the steady-state voltammetric measurement with an ultramicroelectrode. The simulated cyclic voltammogram based on this mechanism was in good agreement with that obtained experimentally. ECL reaction of Ru(bpy)₃²⁺/glyphosate system was found to be strongly dependent on the media pH. In a pH region of 5-9, an ECL wave appeared at ca. +1.1 V vs. Ag/AgCl, which was caused by the generation of *Ru(bpy)₃²⁺ via a Ru(bpy)₃³⁺-mediated oxidation of glyphosate. When pH >10, a second ECL wave was observed at ca. +1.35 V vs. Ag/AgCl, which was believed to be associated with a reaction between Ru(bpy)₃³⁺ and the species from direct oxidation of GLYP at a GC electrode surface.     

零价铁及其复合工艺降解印染废水的应用研究

印染废水因具有高色度、高有机物浓度、难生物降解的独特性质,一直是国内外环境领域关注的重要水体污染源之一。零价铁由于其独特的性质,已成为国内外研究处理印染废水的主要方向之一。介绍了零价铁的研究现状,分析了零价铁降解印染废水的作用机理、动力学及影响因素,着重介绍了近几年新兴的几种零价铁与其他水处理技术联用的复合工艺对印染废水的降解作用。最后,对现存的一些技术问题进行了讨论。     

零价铁材料还原水中硝酸盐的研究进展

硝酸盐（NO3-）是水体中常见的污染物，进入人体后会造成多种损害。零价铁(ZVI)作为一种活性金属，因其高效、无毒、价廉和来源丰富而被广泛用于NO3-的还原。尽管ZVI对硝酸盐有较高的去除效率，但传统ZVI法还原NO3-的主要产物是NH4+，这会对水体造成二次污染。并且由于反应过程中形成的铁氧化物会抑制电子传递，ZVI难以长时间维持高反应活性，对pH有较高的依赖。通过开发或改善现有ZVI复合材料、以及耦合微生物工艺等手段，可降低pH对反应的限制以及还原产物中NH4+的比例，同时将其脱氮性能进一步优化提升，这是目前乃至今后的重点研究方向。该文重点总结了ZVI对NO3-的作用效能和去除机制，阐述了理化特性、pH、温度、溶解氧等因素对ZVI化学反硝化效能的影响，涵盖了ZVI还原硝酸盐的各项性能强化措施。最后归纳了ZVI材料在实际脱氮中需要注意的问题，对其未来发展前景作出了探讨和展望。