纳米零价铁与重金属的反应:“核-壳”结构在重金属去除中的作用

重金属是一类毒性较高、处理难度较大的环境污染物.纳米零价铁因为具有高效分离、固定重金属的潜能而受到广泛关注.其独特的纳米级核壳结构和表面性质使纳米零价铁能够通过吸附、还原和沉淀等多种作用高效去除重金属.现代仪器分析手段的进步,特别是高分辨电子显微成像技术的发展,为深入研究纳米零价铁的微观结构以及纳米零价铁与重金属的作用机理开辟了新的视角.本文重点讨论了纳米零价铁的结构、性质及其在重金属去除中的作用.研究借助高分辨率的球差校正扫描透射电镜(Cs-STEM)成像,配合高灵敏度的X射线能谱仪(XEDS)进行化学分析,旨在更好地了解纳米零价铁的精细结构及其与重金属的界面反应过程和机理.在深入理论研究的同时,通过"小试—中试—工程"逐级放大的方法,系统论证了纳米零价铁处理重金属废水的可行性.结果表明,纳米零价铁可有效、同步去除实际废水中铜、砷、铅、锌等多种重金属,并具有较高的去除负荷.     

纳米零价铁对水中砷和硒去除的比较研究

采用纳米零价铁去除水中的砷和硒,考察了不同溶解氧、纳米零价铁投加量、接触时间以及溶液初始pH值等条件下纳米零价铁去除水中砷和硒的效果,并比较了反应前后固体的形貌、组成、溶液pH值及反应机制.结果表明,纳米零价铁可广泛用于去除水中的砷/硒污染,去除效果顺序依次为Se（IV）> As（Ⅲ）> Se（VI）> As（V）;水中溶解氧（DO）对As（Ⅲ）和Se（IV）的去除没有显著的影响,而高浓度的DO对As（V）和Se（VI）的去除产生了一定的抑制作用;增加纳米零价铁投加量可促进砷和硒的去除;溶液初始pH值对纳米零价铁去除As（Ⅲ）,As（V）和Se（VI）的影响较大,而对Se（IV）的去除几乎没有影响;反应后固体的形貌、组成及溶液pH值存在差异.纳米零价铁与砷、硒反应机理的不同造成了去除效果及反应后固液两相的差异.     

纳米零价铁在水相反应中的表面化学和晶相转化

纳米零价铁在水相中的表面化学特性和晶相等性质变化,将影响其反应活性及环境归趋等.总结近期课题组关于纳米零价铁在水相中表面化学和晶相转化的研究进展,为纳米零价铁污染控制化学提供基础理论.重点探讨水中有无溶解氧、不同水力学条件复氧（静态和扰动）、重金属共存、无机阴离子共存对纳米零价铁颗粒表面化学特性和晶相转变的影响.同时也研究高分子电解质表面修饰后,颗粒在水相中表面及晶相的演变及对重金属去除性能的影响.研究表明,纳米零价铁与水相中的水分子、溶解氧、重金属离子及无机阴离子反应,零价铁失去电子演变为氧化铁、羟基氧化铁等;环境条件对颗粒结构性能产生影响,从而影响污染物去除效率及其在环境中的归趋.未来研究将重点探讨结构性能动态变化与不同污染物之间反应性能的影响,建立纳米颗粒的结构与性能之间关系模型,为纳米零价铁材料的环境应用提供理论依据.     

功能性纳米零价铁的构筑及其对环境放射性核素铀的富集应用研究进展

随着核能的广泛应用和核技术的快速发展,环境中放射性核素铀的污染日益严峻.纳米零价铁（Nanoscale Zero Valent Iron：nZVI）因其具有廉价、制备简便、高表面活性及对铀高效的吸附性能等特性而逐渐成为环境中铀污染处理的良好材料.采用可行的方法制备纳米零价铁复合材料,借助单体材料之间的协同效应可进一步提高材料对铀酰的吸附性能.因此,纳米零价铁复合材料的制备以及应用成为近期环境科学领域的研究热点之一.针对纳米零价铁及其复合材料对环境中铀酰的去除研究进行了概述和展望,包括纳米零价铁及其复合材料的制备方法、去除效果及去除机理,并且简要探讨了纳米零价铁及其复合材料在环境放射性污染治理的应用前景,以期为今后的深入研究和实际应用提供参考依据.     

纳米零价铁复合材料制备、稳定方法及其水处理应用

纳米零价铁(nZVI/Fe⁰)因极高的催化活性和经济适用性备受关注,但实际推广中受团聚性和空气不稳定性等限制。为解决这些问题,近年来国内外学者研究开发了系列纳米零价铁的复合材料和稳定方法,在制备方法、基体材料和环境修复方面均有了较大进展。本文对近五年的研究成果进行汇总,从复合载体研究、稳定方法和水环境应用三个方面对纳米零价铁复合材料研究进行较全面的综述和展望。在纳米零价铁负载方面,本文对聚合物载体、黏土矿物、碳材料和金属氧化物载体的相关研究进行了总结;在颗粒稳定性方面着重讨论了复合金属、表面涂层、硫化方面的新成果;在水环境应用方面,本文指出纳米零价铁主要通过吸附、还原、络合、共沉淀、电化学反应、(类)芬顿氧化等过程实现水中的重金属以及有机物的去除,光、热、电、超声、微波的引入可显著增强水体中污染物的处理效果。     

纳米零价铁活化分子氧原理及降解有机污染物性能增强策略

纳米零价铁直接还原降解有机污染物运行长效性差,且不能矿化有机污染物.利用纳米零价铁还原活化分子氧生成活性氧物种可以氧化甚至矿化有机污染物.在最近的研究中,作者提出了纳米零价铁活化分子氧的双途径机理,即铁核电子转移到氧化铁壳表面的双电子还原活化分子氧途径和氧化铁表面结合态亚铁离子的单电子还原活化分子氧途径,阐释了纳米零价铁核壳结构依赖的分子氧活化降解有机污染物性能机制及性能增强策略.证实在纳米零价铁活化分子氧体系添加少量亚铁离子能在零价铁表面形成更多的结合态亚铁,显著增强纳米铁表界面活性氧物种生成量;同时,在纳米零价铁活化分子氧体系中引入少量有机或无机配体亦可提高活性氧物种产生效率,从而增强有机污染物降解性能.最后讨论了典型环境因素如pH值、共存离子、天然有机物等影响纳米零价铁活化分子氧降解有机污染物性能的规律.     

铁基复合材料的制备及其对水中锑的去除

水体中重金属污染物锑因为具有较高的积累毒性和致癌性而受到研究者的广泛关注。近年来由于世界范围内的锑污染问题日益严峻,因此急需发展经济高效的锑污染处理技术。纳米Fe~0、Fe_3O_4以及FeMnO_x等铁基复合材料凭借其吸附能力强,易分离回收以及安全环保等特点而成为国内外锑污染去除领域的研究热点。本文总结了零价铁和铁氧化物复合材料以及铁基双金属氧化物的制备、改性方法及其对水中污染物锑的去除,重点分析了不同铁基复合材料对Sb(Ⅲ)和Sb(Ⅴ)的吸附机理,总结了温度、p H、共存离子等外界环境对铁基复合材料吸附性能的影响机制,优选了最佳的吸附条件。最后介绍了现有锑污染去除研究中存在的主要问题,展望了铁基复合材料处理水中锑污染物的重点发展方向。     

纳米零价铁去除水体中砷的效能与机理

全球超过一亿人受到高毒性、难处理的砷污染引发的饮用水安全的威胁,解决砷污染问题迫在眉睫而又任重道远。纳米零价铁(nZVI)能高效去除重(类)金属、硝酸盐、磷酸盐、高氯酸盐、卤代物、多环芳烃、偶氮染料和苯酚等污染物,成为广泛应用的工程纳米材料之一,在全球已有近60例的环境原位修复和废水处理工程案例。其独特的纳米级核壳结构和表面性质使其能够通过吸附、还原和沉淀等多种作用高效去砷。本文综述了近年来nZVI及其改性材料去除水中砷的研究进展,探讨了nZVI去除水中As(Ⅲ)和As(Ⅴ)的反应机理,归纳了不同反应条件(初始pH值、反应时间、nZVI投加量、砷初始浓度、共存离子和有机质)对去除效果的影响,总结了nZVI改性材料(多孔材料负载改性nZVI、金属掺杂改性nZVI、表面稳定剂改性nZVI和绿色合成nZVI)对砷的去除效率,展望了纳米零价铁去除砷的发展方向和所面临的挑战。     

硫化纳米零价铁对水中U(VI)的高效去除研究

近年来, 放射性污染物铀(U(VI))在水环境中的排放对生态环境和生物健康造成严重的威胁. 本研究采用液相还原法制备了硫化纳米零价铁(S-NZVI)材料, 并将其用于水中U(VI)的去除. 首先, 我们采取了一系列的微观表征技术探究了S-NZVI的表面特征及材料特性. 结果表明, 相比于纳米零价铁(NZVI), S-NZVI颗粒不易团聚, 性质更加稳定. 随后, 通过宏观实验探究了反应时间、温度、pH、背景离子浓度等因素对S-NZVI去除U(VI)的影响. 结果表明, S-NZVI对U(VI)的最大去除量高达562.5 mg•g^-1, 且在100 min内达到反应平衡. 宏观实验和X射线光电子能谱(XPS)分析表明S-NZVI对U(VI)的去除机理是吸附和氧化还原协同作用的结果. 此外, S-NZVI可以通过外加磁场从水中快速地进行分离, 便于材料再回收与利用. 综上, 本研究构筑了一种制备简单、便于回收且高效的U(VI)净化材料, 未来可能会在放射性核素的处理处置等相关工作中起到重要作用.     

应用纳米零价铁富集银的研究

大量研究表明,纳米零价铁（nanoscale Zero-Valent Iron,nZVI）对水中重金属,尤其是金、银等稀贵金属,有良好的分离富集作用.利用纳米零价铁反应器证明了nZVI可从废水中分离低浓度的银离子（Ag⁺）,并生成高含量的“银矿石”.此外,也证明了反应区氧化还原电位能够反映nZVI与Ag⁺的反应速率和分离效率.利用X射线衍射仪、X射线光电子能谱和高分辨透射电子显微镜等手段对反应产物进行表征,证实了Ag⁺可被nZVI还原为单质银,并以纳米颗粒的形式（<10 nm）沉积在nZVI表面.与其他材料（常见吸附/还原材料）相比,nZVI具有效率高,受pH影响小的优点.研究结果表明,nZVI是一种能够高效富集痕量银资源并产生高价值纳米银的材料.     

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.     

Removal of lead(II) from aqueous solution with amino-functionalized nanoscale zero-valent iron

An effective adsorbent for removal of Pb(II) in aqueous solution was synthesized by reaction of nanoscale zero-valent iron (NZVI) and 3-aminopropyltriethoxysilane (APS). The material was characterized using transmission electron microscopy (TEM), infrared spectroscopy (IR) and a thermogravimetric analyzer (TGA). The amino-coated NZVI rapidly removed Pb(II) from aqueous solution and was easily separated by an external magnetic field. The Freundlich equation was used for investigating the adsorption process of APS-NZVI. Compared to untreated NZVI, the APS-coated NZVI exhibited stronger adsorption affinity and better adsorption performance. Therefore, APS-NZVI may be a suitable material for heavy metal remediation and has potential industrial applications.      

香蕉皮对重金属离子铅的吸附性能研究

建立了香蕉皮快速、高效对重金属离子铅吸附性能的方法。采用分光光度法测定重金属离子铅的浓度,分别研究了7种不同形态的吸附剂对废水中重金属离子铅的吸附性能。在优化的实验条件下,重金属离子铅浓度与吸光度的线性相关系数R=0.999 83,且方法相对标准偏差(RSD)低于3%。结果表明,香蕉皮对废水中的重金属离子铅有良好的吸附效果,吸附率达到91.3%。利用香蕉皮去除废水中的重金属离子,可以变废为宝,且方法吸附率高、准确可靠、精密度高,可用于吸附废水中重金属离子铅。     

Characteristics and Kinetics of Nitrobenzene Reduction by Sucrose-modified Nanoiron

Sucrose-modified nanoscale zero-valent iron(SM-NZVI) was prepared with liquid phase reducing method, and characterized by transmission electron microscopy(TEM) and X-ray diffraction(XRD) for the shape and structure. The size of SM-NZVI particles was about 100―150 nm and they displayed better dispersity. The degradation of nitrobenzene(NB) in water by SM-NZVI was carried out in batch experiments. The results indicate that the efficiency of NB reduction via SM-NZVI increased by 44.24% compared with that via NZVI, and coexistent Ca²⁺, Mg²⁺, HCO₃^- and other ions showed little effect on NB reduction but negative influence on aniline(AN) production. Furthermore, the kinetic researches indicate that NB reduction with SM-NZVI could be described by pseudo first-order kinetic model at different initial pH values and iron dosage. The oxidation products of iron were mainly Fe₃O₄ and Fe₂O₃ with irregular shape.     

Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

Critical Evaluation of Adsorption–Desorption Hysteresis of Heavy Metal Ions from Carbon Nanotubes: Influence of Wall Number and Surface Functionalization

Single‐, double‐, and multi‐walled carbon nanotubes (SWCNTs, DWCNTs, and MWCNTs), and two oxidized MWCNTs with different oxygen contents (2.51 wt % and 3.5 wt %) were used to study the effect of the wall number and surface functionalization of CNTs on their adsorption capacity and adsorption–desorption hysteresis for heavy metal ions (Ni^II, Cd^II, and Pb^II). Metal ions adsorbed on CNTs could be desorbed by lowering the solution pH. Adsoprtion of heavy metal ions was not completely reversible when the supernatant was replaced with metal ion‐free electrolyte solution. With increasing wall number and amount of surface functional groups, CNTs had more surface defects and exhibited higher adsorption capacity and higher adsorption–desorption hysteresis index (HI) values. The coverage of heavy metal ions on the surface of CNTs, solution pH, and temperature affect the metal ion adsorption–desorption hysteresis. A possible shift in the adsorption mechanism from mainly irreversible to largely reversible processes may take place, as the amount of metal ions adsorbed on CNTs increases. Heavy metal ions may be irreversibly adsorbed on defect sites.     

水杨酸型螯合树脂对Fe(III)离子的螯合吸附行为

以5-氨基水杨酸(ASA)为胺化试剂, 使氯甲基化的交联聚苯乙烯(CMCPS)微球表面的苄氯基团发生亲核取代反应, 制得了水杨酸型螯合树脂ASA-CPS. 研究了该螯合树脂对金属离子的螯合吸附行为, 探讨了其吸附热力学与吸附机理, 考察了介质pH值对树脂螯合吸附性能的影响以及树脂对不同金属离子的螯合吸附能力. 实验结果表明, 水杨酸型螯合树脂ASA-CPS 对重金属离子具有强螯合吸附性能, 尤其对Fe3+离子表现出很强的螯合吸附能力, 常温下吸附容量可达21 g/100 g. 吸附过程属熵驱动的化学吸附过程, 升高温度, 吸附容量增高; 在可抑制金属离子水解的pH范围内, 介质的pH值越高, 螯合吸附能力越强; 对于性质不同的金属离子, ASA-CPS的吸附性能是有差别的, 吸附容量的顺序为Fe3+>Ni2+>Cu2+>Zn2+.     

Degradation of nitrobenzene by trisynergetic attapulgite-supported nanoscale zero-valent iron–biofilm

Research on Chemical Intermediates - A trisynergetic system (AFB) of nanoscale zero-valent iron (NI)–biofilm supported on attapulgite (ATP) was used to degrade nitrobenzene (NTB) in aqueous...     

Immobilization of nZVI particles on cotton fibers for rapid decolorization of organic dyes

Nanoscale zero-valent iron (nZVI) particles have been frequently used to treat pollutants as an excellent reactive nanomaterial in last two decades. However, loading nZVI particles on the substrate with large surface area, easy handling and in particular, production on a large scale is still a problem. Herein, a facile approach was developed for in-situ preparation of nanoscale zero-valent iron (nZVI) particles on cotton fibers at room temperature. The cotton fabric was firstly oxidized to generate carboxylic groups for complexing ferric ions. Then, nZVI particles were immobilized on cotton fabric by reducing agent sodium borohydride. The nZVI immobilized cotton fabric (nZVI@cotton fabric) was thoroughly characterized and could decolorize more than 96% methylene blue and brilliant green within 40 min, respectively. The sorption isotherm study revealed that the reactive sorption of methylene blue on nZVI@cotton fabric fits the Freundlich model. The degradation intermediates of methylene blue were identified by HPLC/MS and possible degradation pathway was proposed. The method of immobilizing nZVI particles on carboxylated cotton fibers may be promising to prepare fibrous, easy handling reactive compounds for environmental remediation.

     

The removal and kinetic study of Mn,Fe, Ni and Cu ions from wastewater onto activated carbon from coconut shells

Activated carbon from coconut shells (ACCS) was synthesised and used for the removal of metal ions (manganese, iron, nickel and copper) from aqueous solutions. Two different adsorption models were used for analysing the data. Adsorption capacities were determined: copper ions exhibited the greatest adsorption on activated carbon obtained from coconut shells because of their size and pH conditions. Adsorption capacity varied as a function of the pH. Adsorption isotherms from aqueous solutions of heavy metals on ACCS were determined and were found to be consistent with Langmuir’s adsorption model. Adsorbent quantity and immersion enthalpy were studied. The results were compared with other adsorbents used in a prior study.