纳米零价铁在水处理中的应用研究综述

纳米零价铁(nZVI)作为最常用的纳米颗粒之一,在去除环境水体中的污染物方面开展了大量的研究。本篇综述通过系统全面地总结nZVI的相关进展,介绍nZVI的各个方面进而指导其发展方向。其中,研究内容主要包括制备方法、改性方式、去除不同水中污染物的作用机理和催化机理、在场地研究中的应用以及毒性作用机制。本文发现,纳米零价铁仍存在缺少综合评价方法、应用受限、各项研究不同步等问题。nZVI未来的发展,应具备考虑反应性、稳定性、迁移性、毒性的评价方法,避免同一改性材料在不同研究方向的时间差异性,让nZVI的应用更好地适用实地研究     

纳米零价铁耦合黏土修复污染土壤的研究进展

黏土负载型nZVI具有低成本、易制备、环境相容性好、综合性能优越的特点.本文在归纳nZVI改性策略的基础上,比较了黏土种类对nZVI形貌和性能的影响,提出了理想黏土载体的优选顺序,分析了复合材料的铁含量、比表面积、nZVI尺寸等与去除性能之间的关系,对nZVI耦合黏土在修复土壤重金属、卤代有机物、硝酸盐、新型污染物等方面的研究进行了总结,并概述了nZVI技术在土壤修复中的负面效应,最后对nZVI耦合黏土修复污染土壤的未来方向进行了展望.     

腐植酸对nZVI去除水中Cr(VI)的抑制及抑制作用的消除

以纳米级零价铁(nZVI)为主要工具修复受污染水体中的Cr(VI),考察了腐植酸(HA)对nZVI去除水中Cr(VI)的抑制作用,并初步探讨了淀粉稳定化nZVI对HA抑制作用的消除.结果表明,随着HA初始浓度由0增加大5,10,15,20,30mg/L,反应10min nZVI对Cr(VI)的去除效率分别达到91.9%,82.6%,78.6%,70.4%,70.0 %和69.4 %.可见,HA对nZVI去除Cr(VI)的影响是双方面的,一方面,HA会吸附在nZVI的表面,占据nZVI表面的活性反应部位,导致反应速率的下降;另一方面,HA表面带有大量的活性基团, 有较大的负电性,会起到一定传递电子的作用,进一步促进反应的进行.由于nZVI的比表面积较大,HA的吸附作用占据主导地位, 导致HA的加入对nZVI去除Cr(VI)反应产生明显的抑制作用. 适量淀粉(0.5g/L)的加入确实能够起到阻碍nZVI颗粒团聚和HA在nZVI颗粒表面吸附的作用,从而维持nZVI较高的反应活性,消除HA对nZVI去除Cr(VI)的抑制作用.     

生物炭负载零价纳米铁去除土壤中十溴二苯乙烷

作为十溴联苯醚的替代品,新型溴代阻燃剂十溴二苯乙烷（DBDPE）已经在国内外大量使用.随着DBDPE在各种环境介质中被普遍检测到,其造成的环境污染正引起广泛关注.本论文首先制备生物炭（BC）负载零价纳米铁（nZVI）材料（BC/nZVI）,进而研究了BC/nZVI去除土壤中DBDPE的动力学过程,并探究了作用机制.结果表明：BC加入能促进nZVI均匀分散在生物炭的表面,并改善了其分散程度;BC/nZVI去除效率最高（投加量为0.1 g·g^-1,BC：nZVI为2：1,DBDPE初始浓度为10 mg·kg^-1）,24 h内达到了89.74%,去除过程涉及到吸附和降解的共同作用,实验数据符合准一级动力学方程;采用LC-MS-MS探究了DBDPE的降解产物和途径;ECOSAR毒性评价数据显示BC/nZVI能够降低DBDPE的生态毒性.     

Performance of bimetallic nanoscale zero-valent iron particles for removal of oxytetracycline

In this study, bimetallic nanoscale zero-valent iron particles(nZVI), including copper/nanoscale zero-valent iron particles(Cu/nZVI) and nickel/nanoscale zero-valent iron particles(Ni/nZVI), were synthesized by one-step liquid-phase reduction and applied for oxytetracycline(OTC) removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray diffraction(XRD). Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy(XPS) and mass spectrometry(MS). Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC(100 mg/L) in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.     

纳米零价铁的制备技术及其应用研究进展

纳米零价铁（nZVI）因具有还原性强、粒径小、比表面积大等特性,对重金属及含卤有机污染物等具有良好的吸附特性和反应活性,在环境修复方面表现出较好的应用前景。但nZVI易氧化、团聚和机械强度低等不利因素限制了其大规模应用。系统比较了机械法、气体冷凝法及还原法制备nZVI技术的特点,重点总结表面改性、金属改性、载体负载和基质封装等手段制备改性nZVI的研究进展,及其在水体及土壤环境修复方面的应用。     

Microbes team with nanoscale zero-valent iron: A robust route for degradation of recalcitrant pollutants

Integrating nanoscale zero-valent iron (nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano- and bio-technologies. nZVI and microbes can perform in coalition in direct contact and act simultaneously, or be maintained in separate reactors and operated sequentially. Both modes can generate enhanced performance for wastewater treatment and environmental remediation. nZVI scavenges and eliminates toxic metals, and enhances biodegradability of some recalcitrant contaminants while bioprocesses serve to mineralize organic compounds and further remove impurities from wastewater. This has been demonstrated in a number of recent works that nZVI can substantially augment the performance of conventional biological treatment for wastewaters from textile and nonferrous metal industries. Our recent laboratory and field tests show that COD of the industrial effluents can be reduced to a record-low of 50 ppm. Recent literature on the theory and applications of the nZVI-bio system is highlighted in this mini review.     

碳基材料负载纳米零价铁去除六价铬的研究进展

近年来,纳米零价铁(nZVI)因具有比表面积大、还原能力强、成本低的特点被用于去除环境中的六价铬〔Cr(Ⅵ)〕,然而由于高表面能、固有磁力等因素的影响,nZVI具有易团聚、易氧化和不稳定的缺点,限制了其广泛应用. 鉴于此,本文以碳材料作为支持材料改性nZVI,比较了制备碳基nZVI复合材料的方法,分析了不同碳基nZVI复合材料去除Cr(Ⅵ)的反应效能,阐述了影响复合材料去除Cr(Ⅵ)的因素. 结果表明:①湿化学法合成的复合材料有利于提高nZVI的分散性,减少团聚. 热转化法合成的复合材料有利于节约成本,提高碳材料和nZVI的结合性. ②不同碳材料负载nZVI能有效提高nZVI的分散性、稳定性和抗氧化性. ③碳基材料负载nZVI能有效降低环境因素对nZVI的负面影响. ④碳基nZVI复合材料能提高对Cr(Ⅵ)的去除能力,其对Cr(Ⅵ)的最大吸附容量比nZVI高1.2～20倍. 本文旨在深入了解碳基nZVI复合材料的合成方法,提高碳基nZVI复合材料的性能,以期为开发高效稳定的碳基nZVI复合材料修复环境中的Cr(Ⅵ)提供一些启示.      

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron: Synergetic effect, efficiency optimization and mechanism

In this study, a novel nanoscale zero-valent iron (nZVI) composite material was successfully synthesized using a low-cost natural clay, “Hangjin 2^# clay” (HJ clay) as the support and tested for the decolorization of the azo dye Methyl Orange (MO) in aqueous solution by nZVI particles. According to the characterization and MO decolorization experiments, the sample with 5:1 HJ clay-supported nZVI (HJ/nZVI) mass ratio (HJ-nZVI5) showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe⁰ dosage, the HJ-nZVI1 and HJ-nZVI5 samples demonstrated a synergetic effect for the decolorization of MO: their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and nZVIs, or the sum of HJ clay and nZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the nZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-nZVI dosage, higher temperature and under N₂ atmosphere, while the MO initial concentration and pH were negatively correlated to the efficiency. HJ clay not only works as a carrier for nZVI nanoparticles, but also contributes to the decolorization through an “adsorption-enhanced reduction” mechanism. The high efficiency of HJ-nZVI for decontamination gives it great potential for use in a variety of remediation applications.     

纳米零价铁还原溴代阻燃剂的进展研究

地表水、地下水和土壤污染是当今社会人类生存面临的主要问题.由于溴代阻燃剂的广泛应用以及它们的难降解性、毒性和蓄积性等特性,成为水体和土壤的严重污染源.纳米零价铁比表面积大、还原性强、价格低廉且毒性小,通过零价铁有效还原转化来降低溴代阻燃剂的毒性是一项有前景的环境修复技术.对纳米零价铁的制备、改性和环境应用进行了介绍,系统探讨了纳米零价铁还原溴代阻燃剂的研究成果和现状,并对其发展前景进行了展望.     

还原氧化石墨烯支撑纳米零价铁对含Sb(Ⅲ)废水的处理

针对含重金属Sb(III)废水处理问题,采用液相还原法制备出高效的还原氧化石墨烯负载纳米零价铁(nZVI/rGO)复合吸附材料,并采用多种技术手段对所制备的nZVI/rGO复合材料进行表征.同时,复合材料中nZVI的负载量、吸附剂投加量、初始pH值以及反应温度等因素对废水中Sb(Ⅲ)吸附去除效果的影响被全面考察,并进一步对吸附过程进行吸附等温线和吸附动力学拟合.结果表明,在25℃,pH为3.0时,当nZVI负载量为70wt%,nZVI/rGO投加量为0.5g/L时,Sb(Ⅲ)的去除率最高,140min内可达99.7%.该吸附过程符合准二级动力学模型与Langmuir等温吸附模型,因此nZVI/rGO被证实是一种高效的Sb(III)吸附材料.     

零价纳米铁吸附去除水中六价铬的研究

利用液相还原法制备的零价纳米铁(nZVI)进行了去除水中Cr(Ⅵ)的实验研究.结果表明,nZVI对Cr的去除效果明显优于还原铁粉和粉末活性碳;pH值越小、初始Cr浓度越低、nZVI放置时间越短及投加量越大均有利于水中Cr(Ⅵ)的去除,最佳去除率近100%;反应动力学拟合结果表明,nZVI去除六价铬符合准二级动力学模型;反应后nZVI颗粒的扫描电镜及电子能谱结果显示Cr占12.02%(wt),结合对反应溶液中Cr(Ⅵ)和Cr(Ⅲ)分析,说明吸附、还原与共沉淀可能是nZVI去除水中六价铬的主要机理.     

Graphene-supported nanoscale zero-valent iron：Removal of phosphorus from aqueous solution and mechanistic study

Excess phosphorus from non-point pollution sources is one of the key factors causing eutrophication in many lakes in China,so finding a cost-effective method to remove phosphorus from non-point pollution sources is very important for the health of the aqueous environment. Graphene was selected to support nanoscale zero-valent iron(nZVI)for phosphorus removal from synthetic rainwater runoff in this article. Compared with nZVI supported on other porous materials,graphene-supported nZVI(G-nZVI) could remove phosphorus more efficiently. The amount of nZVI in G-nZVI was an important factor in the removal of phosphorus by G-nZVI,and G-nZVI with 20 wt.% nZVI(20% G-nZVI)could remove phosphorus most efficiently. The nZVI was very stable and could disperse very well on graphene,as characterized by transmission electron microscopy(TEM) and scanning electron microscopy(SEM). X-ray photoelectron spectroscopy(XPS),Fourier Transform infrared spectroscopy(FT-IR) and Raman spectroscopy were used to elucidate the reaction process,and the results indicated that Fe-O-P was formed after phosphorus was adsorbed by G-nZVI. The results obtained from X-ray diffraction(XRD) indicated that the reaction product between nZVI supported on graphene and phosphorus was Fe3(PO4)2·8H2O(Vivianite). It was confirmed that the specific reaction mechanism for the removal of phosphorus with nZVI or G-nZVI was mainly due to chemical reaction between nZVI and phosphorus.     

粉煤灰基多孔材料负载纳米铁的制备及其对龙胆紫的去除效果

为制备新型可再生吸附反应材料,以工业废弃物粉煤灰、棕榈壳等为主要原料,烧结制备FAP（粉煤灰基多孔材料）,并以FAP为载体负载纳米零价铁,制备FAP/nZVI（粉煤灰基纳米零价铁多孔材料）,以散失率、龙胆紫去除率、纳米零价铁负载量等为指标,确定FAP及FAP/nZVI的最佳制备条件,并考察二者对染料龙胆紫的去除特性.结果表明:① FAP的最佳制备条件为m（粉煤灰）:m（膨润土）:m（棕榈壳）=190:95:15,升温速率10℃/min,烧结温度800℃,保温时间30 min.② FAP/nZVI最佳制备条件为m（Fe）/m（FAP）1:3,振荡时间1 h,选用抗坏血酸为稳定剂,过程中无需使用惰性气体;SEM结果表明纳米零价铁被成功负载于FAP上.③ FAP/nZVI对200 mg/L龙胆紫的去除率为94.8%,FAP同条件下的去除率仅为26.2%,FAP/nZVI对龙胆紫的去除同时存在物理吸附和化学还原作用,并且纳米零价铁的还原占主导作用.④ FAP/nZVI再生10次后30 min内对100 mg/L龙胆紫去除率高达97.6%.研究显示,FAP可将纳米零价铁氧化产物Fe2+固定在表面,经还原后可再生为纳米零价铁,具有良好的再生性能.      

nZVI@SiO2-NH2对合成染料脱色效果及其对大肠杆菌生物毒性研究

采用液相还原法并使用氨基修饰的二氧化硅合成包覆型的纳米零价铁(nZVI@SiO_2-NH_2),同时,采用XRD、FT-IR及TEM等多种方法对所制备的材料进行表征.TEM表征结果表明,nZVI@SiO_2-NH_2粒径分布在10～50 nm之间,壳层厚度为15 nm.XRD和FTIR分析表明,复合颗粒具有Fe~0晶型结构的内核,表面SiO_2壳层存在氨基化修饰.使用nZVI@SiO_2-NH_2和nZVI对各类染料进行脱色处理,结果表明,nZVI@SiO_2-NH_2对上述染料的脱色效果都优于nZVI,且nZVI@SiO_2-NH_2具有对染料进行连续脱色的能力.大肠杆菌的存活情况和细胞内酶LDH和SOD的活性变化表明,nZVI@SiO_2-NH_2对生物的毒性更小.     

Immobilization and transformation of co-existing arsenic and antimony in highly contaminated sediment by nano zero-valent iron

Arsenic(As) and antimony(Sb) are usually coexistent in mine wastes and pose a great threat to human health. The As immobilization by nano zero-valent iron(n ZVI) is promising, however, the stabilization for co-occurring As and Sb is not known. Herein, the immobilization and transformation of As and Sb in n ZVI-treated sediments were evaluated using complementary leaching experiments and characterization techniques. Raw sediment samples from a gold-antimony deposit revealed the co-existence of ul...     

多聚物吸附纳米零价铁在多孔介质中的迁移

针对纳米零价铁在多孔介质中的迁移特点,本文通过实验室柱实验和腐蚀实验分析了不同聚丙烯酸（PAA）包覆浓度下的纳米零价铁（nZVI）在石英砂介质中的迁移和其接触不同电解质溶液6h的反应活性.利用迁移距离和穿出率,表征了不同纳米铁材料的迁移性能.应用pH值、氧化还原电位（ORP）、Fe²⁺浓度、X射线衍射（XRD）和Fe⁰含量随时间变化图像表征纳米零价铁腐蚀程度.实验结果表明,PAA显著提高了纳米零价铁材料的迁移距离.10%聚丙烯酸包覆浓度下,实验室合成纳米零价铁的迁移效果最佳,穿出率可达58.65%.在6h的腐蚀实验中,10%聚丙烯酸包覆的零价铁含量有一定的降低,但是零价铁损失相对于20% PAA包覆的零价铁少.综合考虑迁移性和反应活性,10% PAA包覆浓度下实验室合成纳米零价铁是适用于地下水污染原位修复的最佳材料.     

制备工艺对nZVI/污泥基生物炭中Zn、Cu、Pb形态分布及其生态风险的影响

以市政污泥为原料、纳米零价铁（nZVI）为添加剂,采用热解法制备污泥生物炭,考察了nZVI添加量、热解温度和升温速率对生物炭中Zn、Cu、Pb形态分布及其生态风险的影响。结果显示:高nZVI添加量、高热解温度及低升温速率可提高稳定态（BCR法） Zn、Cu和Pb的含量;高nZVI添加量可促使Zn、Cu和Pb向可氧化态转化,而高热解温度和低升温速率有利于残渣态Zn、Cu和Pb的生成;最优nZVI添加量、热解温度和升温速率分别为2000 mg/kg,800℃和4℃/min。此外,当nZVI添加量为800 mg/kg、热解温度为800℃和升温速率为2℃/min时有利于降低Zn、Cu和Pb的生态风险;Zn、Cu和Pb总体生态风险等级分别为低风险、低风险和无风险,与Cu和Pb相比,Zn的生态风险较高;以RI值为评价指标,nZVI/污泥基生物炭的优化制备工艺为:nZVI添加量为200 mg/kg,热解温度为800℃,升温速率为5℃/min。     

纳米零价铁对升流式颗粒污泥床反硝化性能的影响

为探究连续流条件下,纳米零价铁(nZVI)对反硝化颗粒污泥(DGS)性能的影响,本文利用升流式污泥床(USB),系统考察了反应器脱氮效能、污泥形态和反硝化特性随进水nZVI浓度的变化规律.结果表明,当nZVI5 mg·L~(-1)时,反应器脱氮效能与对照期(nZVI=0 mg·L~(-1))相差很小,DGS活性略微增大.当nZVI浓度在5~10 mg·L~(-1)时,DGS对nZVI的生物抑制作用表现出一定适应性,污泥浓度和颗粒粒径仍保持增长趋势,但泥相中总铁含量明显增大,DGS活性开始降低.当nZVI浓度增至30 mg·L~(-1)时,反应器对COD和NO-3-N的去除率分别降至对照期的23.3%和20.3%.DGS因吸附大量nZVI而呈黑色,颗粒粒径减小,污泥表面短杆菌等微生物密度明显降低.停止投加nZVI后,污泥浓度与DGS活性的持续上升,使得反应器脱氮效能在20 d内基本恢复至对照期的水平.异养菌在颗粒表面的快速增殖是实现上述目标的主要原因.     

纳米零价铁铜双金属体系对土壤中四氯双酚A的降解

纳米零价铁及其双金属材料因比表面积大、反应活性高,已被大量应用于地下水中卤代有机污染物、无机盐和重金属的处理,而将纳米零价铁铜双金属(Cu/n ZVI)应用于四氯双酚A(TCBPA)污染土壤的修复却鲜见报道.本文以Cu/nZVI为反应材料,探究了TCBPA起始浓度,Cu/n ZVI投加量、p H、温度等因素对土壤中TCBPA降解率的影响.批实验结果表明:反应温度为25℃,经过360 min的反应后,0.30 g的Cu/n ZVI对土壤中0.8 mg·g~(-1)TCBPA的降解率可达85%以上.Cu/n ZVI对土壤中TCBPA的降解率随TCBPA初始浓度的增加而降低,随Cu/n ZVI投加量的增加而升高,随土壤初始p H的增加而降低,Cu/n ZVI对TCBPA的降解在常温条件下即可有效的进行.Cu/nZVI对TCBPA的降解遵循准一级反应动力学模型.GC-MS结果表明,Cu/n ZVI降解TCBPA是一个逐步还原脱氯的过程.