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.     

硫化纳米零价铁对PCB153的降解研究

硫化纳米零价铁(S-nZVI)是近年来兴起的一种纳米零价铁改性材料,已有研究发现其在重金属污染物去除方面具有较好的效果,而有关其对多氯联苯(PCBs)的反应活性目前尚未见报道.因此,本研究对比了采用前置硫化合成法制备的S-nZVI(S/Fe=0.103)、纳米零价铁(nZVI)和羧甲基纤维素稳定纳米零价铁(CMC-nZVI)3种纳米零价铁材料降解六氯联苯PCB153的反应动力学,研究了pH值、阴离子、腐殖酸(HA)等因素对该反应的影响,分析了反应前后材料表面性质的变化,探讨了脱氯路径和反应机理.结果表明,3种纳米零价铁材料对PCB153的降解反应符合准一级动力学,降解机理相似,降解效果依次为CMC-nZVInZVIS-nZVI.硫化改性降低了nZVI去除PCB153的反应活性,S-nZVI表面的硫铁化物并未直接参与PCB153降解反应,S-nZVI反应活性低的原因可能是硫铁化物的形成损耗了一部分Fe~0的还原能力.此外,与CMC-nZVI、nZVI不同,高pH更有利于S-nZVI对PCB153的降解,阴离子和HA对3种纳米零价铁活性的影响规律相似.研究结果可为S-nZVI在持久性有机污染物降解中的应用提供理论依据和技术支持.     

白腐菌联合纳米零价铁强化去除水中Cd(II)

采用白腐菌和纳米零价铁(nZVI)联合体系强化去除水中Cd (II),并考察pH值、Cd (II)初始浓度、温度、nZVI投加量对Cd (II)去除的影响,分析nZVI对白腐菌胞内外富集镉的影响特性,同时结合扫描电镜、红外光谱、X射线光电子能谱、三维荧光光谱等手段分析联合体系对Cd (II)的强化去除机制.结果表明,在pH=6,Cd (II)初始浓度为50mg/L,温度为30℃,nZVI投加量为0.1g/L的条件下反应180min后,Cd (II)的去除率可达到99.5%以上.联合体系对Cd (II)的去除过程符合准二级动力学,主要去除机制为白腐菌对Cd (II)的胞外络合吸附,添加nZVI能促进白腐菌对Cd (II)的胞外吸附,FTIR和XPS分析表明,羟基、羧基和氨基参与了Cd (II)的吸附,白腐菌胞外聚合物(EPS)能与铁发生内层配位形成P-O-Fe键,加速富含羟基官能团的纤铁矿、磁铁矿等铁矿物形成,从而促进对溶液中Cd (II)的吸附去除.     

铁基双金属强化降解地下水中四氯化碳

采用沉积置换法制备了微米级的Ni-Fe、Cu-Fe、Ag-Fe双金属颗粒，应用扫描电镜（SEM）、X射线光电子能谱（XPS）分析了其表面特征，考察了负载金属类型、金属负载量对铁基双金属降解四氯化碳（CCl₄）的影响.结果表明：Ni、Cu、Ag等催化金属非均匀地负载在铁基体上，双金属颗粒表面发生了氧化.CCl₄的降解速率对催化金属的负载量比较敏感，双金属体系Ni、Cu、Ag的适宜负载量分别为1.0wt%、0.8wt%和0.4wt%.CCl₄在双金属体系中的降解途径为零价铁颗粒表面的直接还原及催化金属表面的催化加氢还原，以催化加氢还原为主.Ni-Fe、Cu-Fe、Ag-Fe对CCl₄的还原降解速率大小顺序与其电偶电池电动势的大小顺序一致，即Ag-Fe对CCl₄的降解速率最快，Cu-Fe次之，Ni-Fe最慢.     

Wastewater degradation by iron/copper nanoparticles and the microorganism growth rate

Nowadays, trends in wastewater treatment by zero-valent iron (ZVI) were turned to use bimetallic NZVI particles by planting another metal onto the ZVI surface to increase its reactivity. Nano size zero-valent iron/copper (NZVI/Cu⁰) bimetallic particles were synthesized in order to examine its toxicity effects on the wastewater microbial life, kinetics of phosphorus, ammonia stripping and the reduction of chemical oxygen demand (COD). Various concentrations of NZVI/Cu⁰ and operation conditions both aerobic and anaerobic were investigated and compared with pure NZVI experiment. The results showed that addition 10 mg/L of NZVI/Cu⁰ significantly increased the numbers of bacteria colonies under anaerobic condition, conversely it inhibited bacteria activity with the presence of oxygen. Furthermore, the impact of nanoparticles on ammonia stripping and phosphorus removal was also linked to the emitted iron ions electrons. It was found that dosing high concentration of bimetallic NZVI/Cu⁰ has a negative effect on ammonia stripping regardless of the aeration condition. In comparison to control, dosing only 10 mg/L NZVI/Cu⁰, the phosphorus removal increased sharply both under aerobic and anaerobic conditions, these outcomes were obtained as a result of complete dissolution of bimetallic nanoparticles which formed copper-iron oxides components that are attributed to increasing the phosphorus adsorption rate.     

Kinetics of Solvent Blue and Reactive Yellow removal using microwave radiation in combination with nanoscale zero-valent iron

We investigated the efficiency and kinetics of the degradation of soluble dyes over the p H range 5.0–9.0 using a method employing microwave radiation in combination with nanoscale zero-valent iron(MW–n ZVI). The n ZVI particles(40–70 nm in diameter) were prepared by a liquid-phase chemical reduction method employing starch as a dispersant.Compared to the removal of Solvent Blue 36 and Reactive Yellow K-RN using only n ZVI,more rapid and efficient dye removal and total organic carbon removal were achieved using MW–n ZVI. The dye removal efficiency increased significantly with decreasing p H, but was negligibly affected by variation in the microwave power. The kinetics of dye removal by MW–n ZVI followed both an empirical equation and the pseudo first-order model, while the kinetics of dye removal using n ZVI could only be described by an empirical equation. It was also concluded that microwave heating of the dye solutions as well as acceleration of corrosion of n ZVI and consumption of Fe(II) were possible reasons behind the enhanced dye degradation.     

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.     

有机凹凸棒石负载纳米零价铁去除水中六价铬

以黏土为载体负载纳米零价铁（nZVI,nanoscale zero-valent iron）可改善零价铁颗粒的团聚行为,增强其反应性.在负载过程中铁和黏土用量比例不同,对nZVI颗粒团聚和反应性的影响也不同.以有机凹凸棒石（CTMAB/A）为载体,采用液相还原法在1：3和1：5两种铁土质量比条件下制备负载型纳米零价铁复合材料CTMAB/A-nZVI-3和CTMAB/A-nZVI-5.利用X射线衍射仪（XRD）和扫描电子显微镜（SEM）表征了两种负载样品和不添加黏土载体时nZVI的分散差异,并通过X射线光电子能谱仪（XPS）分析样品与Cr（VI）反应后的产物分布.结果表明：降低负载反应时的铁土比能明显改善nZVI粒子的团聚现象、减小nZVI平均粒径、提高小粒径颗粒占比、增强其反应活性.小于10nm的nZVI颗粒在CTMAB/A-nZVI-3和CTMAB/A-nZVI-5负载nZVI总数中占比分别为3.60%和7.60%,在不负载的nZVI样品中占比为0.铁的投加量同为0.75g/L时,CTMAB/A-nZVI-5中铁对Cr（VI）去除率为86.20%,CTMAB/A-nZVI-3中为78.00%.     

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.     

纳米单质铁对厌氧氨氧化脱氮性能的影响

通过向厌氧氨氧化反应器(ASBR)中投加纳米单质铁(nZVI),考察了其对厌氧氨氧化反应(ANAMMOX)脱氮性能的影响.结果表明,在温度为(25±0.5)℃,pH值为7.5±0.5,进水NH₄⁺-N和NO₂^--N浓度分别为30.35mg/L和37.89mg/L条件下,分别投加0,10,50,100.200,500,1000mg/L nZVI时,总氮去除率(NRE)分别达到70.27%、74.25%、83.45%、90.16%、68.59%、57.18%、50.93%.用修正的Boltzmann、Gompertz、Logistic模型对其进行动力学分析,R²值分别为0.9963、0.9944、0.9851,总氮(TN)出水浓度和NRE的预测值与实际值比较,其均方误差值分别为2.13、6.31、8.48和6.93、7.47、10.95.     

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.     

纳米镍/铁和铜/铁双金属对四氯乙烯脱氯研究

以实验室合成的纳米双金属颗粒(Ni/Fe和Cu/Fe)为反应材料,对四氯乙烯(PCE)进行脱氯试验研究.纳米金属颗粒(直径范围在1～100nm)比表面积比微米级铁颗粒高数十倍.结果表明,纳米Ni/Fe和Cu/Fe对四氯乙烯有明显的脱氯作用,且脱氯反应符合准一级反应动力学方程;在作为还原剂的铁表面镀上一薄层起催化作用的金属Ni或Cu,催化剂的存在大大降低脱氯反应活化能,提高了脱氯速率,并减少氯代副产物的产量.与零价铁及微米级双金属系统(Ni/Fe,Cu/Fe)相比,纳米颗粒对PCE的脱氯速率有明显提高,尤其是纳米Ni/Fe,标准化反应速率常数KSA为4.283 mL·m-2·h-1,分别比零价铁和微米级Ni/Fe系统快33.23倍和11.59倍.纳米Cu/Fe标准化反应速率常数KSA为1.194 mL·m-2·h-1,分别比零价铁和微米级Cu/Fe双金属系统快9.26倍和5.24倍.在相同条件下,纳米Ni/Fe脱氯速率常数KSA是纳米Cu/Fe的3.59倍.     

可迁移性零价铁的制备及其活化过硫酸盐氧化修复石油污染土壤

纳米零价铁(nZVI)活化过硫酸盐(PS)体系具有活性高、持效性长等潜在优势,在有机污染土壤修复领域具有良好的应用前景.然而,nZVI颗粒易于发生团聚和被空气氧化,在土壤中迁移性能和稳定性能较差,限制了其活化性能的发挥.本研究采用聚天冬氨酸(PASP)修饰和硫化改性技术,制备了可迁移的零价铁复合材料(PASP-S-nZVI),评价了PASP-S-nZVI的活化PS性能及其在石英砂填充介质中的迁移性能,优化了该材料活化PS降解土壤中石油烃的反应条件,并开展了土壤污染修复小试试验. SEM-EDS和XPS表征结果显示,PASP-S-nZVI材料为表面具有PASP涂层及硫铁化物(FeS_x)的零价铁.与未改性nZVI和S-nZVI相比,PASP-S-nZVI材料的悬浮稳定性、Zeta电位和电子利用率都显著增加,表明双重改性增加了nZVI的稳定性能.柱试验结果显示,PASP-S-nZVI具有较低的附着效率,其实际碰撞效率是S-nZVI的38.0%、nZVI的26.5%,在含水介质中的迁移性能显著增加,且增加程度与填充介质的粒径尺寸和水体pH有关.在优化的条件参数下,PASP...     

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.     

包覆型纳米铁的制备及其降解三氯乙烯的性能研究

采用甲基丙烯酸甲酯(MMA)为聚合单体,偶氮二异丁腈(AIBN)为引发剂,通过微乳液原位聚合法制备包覆型纳米铁,采用XRD、FI-IR、TEM对其性能进行表征.结果表明:包覆型纳米铁(En-n ZVI)是在纳米铁颗粒(n ZVI)外层形成了稳定的聚甲基丙烯酸甲酯(PMMA)包覆层,包覆后的纳米铁粒径均一、不团聚,并能于空气中放置3 d以上而不被氧化,克服了纳米铁在空气中不能稳定存在的缺点.降解实验结果表明:该纳米材料能有效降解环境污染物三氯乙烯TCE,24 h去除率超过了92%,脱氯率达到90.0%.     

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.     

海藻酸钠固定化纳米铁还原脱色活性红X3B

采用海藻酸钠固定纳米铁制备海藻酸钠纳米铁小球,研究了海藻酸钠浓度、纳米铁含量、活性红X3B浓度、反应温度、pH值等对海藻酸钠固定化纳米铁小球还原活性红X3B的影响.采用高效液相色谱（HPLC）、紫外可见分光光度计（UV-Vis）、扫描电镜（SEM）、透射电镜（TEM）等方法分析污染物的还原脱色过程.结果表明,X3B的还原脱色获得了较好的效果,当温度25.0℃,海藻酸钠浓度2.0%,纳米铁含量2.0g/L,转速200r/min,pH值10.9时,反应720min后,25.0mg/L活性红X3B的脱色率达98.9%.海藻酸钠凝胶对活性红X3B没有吸附作用,海藻酸钠固定化纳米铁小球降解活性红X3B的主要机制为纳米零价铁的还原作用.     

Mobility and sulfidization of heavy metals in sediments of a shallow eutrophic lake, Lake Taihu, China

The technique of DGT (diffusive gradients in thin films) using three diffusive gel thicknesses was applied to estimate the mobility and bioavailability of heavy metals in sediments and porewater of Lake Taihu, China. The DGT results showed significantly positive correlations between Co, Pb, Cd and Mn, and Ni and Fe concentrations in porewater. Cu and Zn showed a significantly negative correlation with Mn, due to Cu combination with carbonates and Zn derived from agricultural pollution, respectively. The rank order of average concentrations of Co, Ni and Cd at each station was DGT_1.92 > DGT_0.78 > DGT_0.39, suggesting stronger resupply from sediments to porewater when using thicker diffusive gels. Comparing centrifugation and DGT measurements, Co, Ni and Cd are highly labile; Mn and Fe are moderately labile; and Cu, Zn and Pb are slightly labile. The variations of AVS concentrations in sediment cores indicate that metal sulfides in deeper layers are easily diffused into surface sediments.     

铁纳米线对水中Cu2+的吸附性能及机理

为研究nZVI（纳米零价铁）材料对水中Cu2+的吸附性能,采用液相还原法合成核壳结构的nZVI,即FSCNs（铁纳米线,Fe@Fe₂O₃ core-shell nanowires）.通过批处理吸附试验研究pH、离子强度、FSCNs投加量、反应时间、初始ρ（Cu2+）、反应温度等因素对Cu2+去除率的影响,运用动力学模型、等温吸附模型和吸附热力学模型分析FSCNs对Cu2+的吸附特性,并利用SEM（扫描电镜）、XRD（X射线衍射）和XPS（X射线光电子能谱）等表征手段探讨FSCNs对Cu2+的吸附机制.结果表明:①在pH为5、离子强度为0.01 mol/L、FSCNs投加量为0.5 g/L、反应温度为318 K条件下,FSCNs对Cu2+产生的吸附容量最大,为387.6 mg/g.②FSCNs对Cu2+的吸附反应在30 min内达到吸附平衡,此时的最大吸附率可达96%;FSCNs对Cu2+的吸附更符合准二级动力学模型（R2≥0.992）,表明化学吸附可能为该反应的限制步骤;Langmuir和Freundlich等温吸附模型均能较好地拟合吸附结果（R2≥0.992）;该吸附过程是自发的吸热反应〔ΔG0（吉布斯标准自由能） < 0,ΔH0（标准焓变）>0〕.③大部分Cu2+在加入FSCNs后转化为Cu、Cu₂O和CuO,被吸附在FSCNs表面,吸附、还原与共沉淀可能是FSCNs去除水中Cu2+的主要机理.研究显示,FSCNs对Cu2+的最大吸附容量为387.6 mg/g,能快速高效吸附水中的Cu2+,应用前景良好.      

纳米零价铁基生物炭活化过硫酸盐降解土霉素

采用纳米零价铁基生物炭(nZVI-BC)耦合过二硫酸钠(PDS)或过硫酸氢钾(PMS)构建吸附-高级氧化复合体系开展水中土霉素(OTC)的高效降解。考察了在不同PDS/PMS浓度、nZVI-BC投量、OTC浓度及初始pH条件下OTC的去除规律,并对体系中活性物种进行探究。结果表明:在0.20 mmol/L PDS/PMS,0.01 g nZVI-BC,50 mg/L OTC,原始pH为5.0±0.1条件下,OTC去除率可达到80%以上;SO₄-·在nZVI-BC/PDS体系中对OTC降解占有绝对主导地位(贡献度为57.00%),nZVI-BC/PMS体系则主要依靠SO₄-·、O₂-·和1O₂。