Rapid decolorization of Acid Orange II aqueous solution by amorphous zero-valent iron

Some problems including low treatment capacity, agglomeration and clogging phenomena, and short working life, limit the application of pre-treatment methods involving zero-valent iron (ZVI). In this article, ZVI was frozen in an amorphous state through a melt-spinning technique, and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature, ribbon dosage, and initial pH. Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage, but decreased with increasing initial solution pH. Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model, and the surface-normalized decolorization rate could reach 2.09 L/(m². min) at room temperature, which was about ten times larger than any previously reported under similar conditions. Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency. This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.     

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily. __________ Translated from China Environmental Science, 2006, 26(6): 698–702 [译自: 中国环境科学]     

Stabilization of nanoscale zero-valent iron in water with mesoporous carbon (nZVI@MC)

Two challenges persist in the applications of nanoscale zero-valent iron(nZVI) for environmental remediation and waste treatment: limited mobility due to rapid aggregation and short lifespan in water due to quick oxidation. Herein, we report the nZVI incorporated into mesoporous carbon(MC) to enhance stability in aqueous solution and mobility in porous media. Meanwhile, the reactivity of nZVI is preserved thanks to high temperature treatment and confinement of carbon framework. Small-sized(～16 nm) nZVI nanoparticles are uniformly dispersed in the whole carbon frameworks. Importantly, the nanoparticles are partially trapped across the carbon walls with a portion exposed to the mesopore channels. This unique structure not only is conductive to hold the nZVI tightly to avoid aggregation during mobility but also provides accessible active sites for reactivity. This new type of nanomaterial contains ～10 wt% of iron. The nZVI@MC possesses a high surface area(～ 500 m~2/g) and uniform mesopores(～ 4.2 nm) for efficient pollutant diffusion and reactions. Also, high porosity of nZVI@MC contributes to the stability and mobility of nZVI. Laboratory column experiments further demonstrate that nZVI@MC suspension(～4 g Fe/L) can pass through sand columns much more efficiently than bare nZVI while the high reactivity of nZVI@MC is confirmed from reactions with Ni(II). It exhibits remarkably better performance in nickel(20 mg/L) extraction than mesoporous carbon, with 88.0% and 33.0%uptake in 5 min, respectively.     

纳米零价铁降解水中四氯化碳的试验研究

以四氯化碳为目标污染物,研究了不同因素对自制纳米零价铁降解水中四氯化碳的影响,并对反应产物及可能的反应路径进行了探讨.结果表明,自制纳米零价铁对四氯化碳有很好的降解效果.在pH=3和30℃的条件下,当初始四氯化碳浓度为2.0 mg·L~(-1),纳米零价铁浓度为1.0 g·L~(-1)时,去除率高达96.7%.纳米零价铁降解四氯化碳的酸碱适应范围较大(pH值3~9).随着温度升高和纳米零价铁投加量的增大,四氯化碳降解率显著提高.该反应符合一级动力学,且反应活化能较低,反应易于进行.     

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.     

杭锦土负载硫化零价铁的研制及除磷性能

以具有较大比表面积和良好吸附性能的天然杭锦土为载体制备杭锦土负载硫化零价铁（HJ@S-nZVI）。优化铁负载比、硫铁摩尔比（S/Fe）以及陈化时间等制备条件,利用扫描电子显微镜（SEM）、能量色散光谱(energy dispersive spectroscopy,EDS)、X射线光电子能谱（XPS）及比表面积（specific surface area,SSA）等手段对HJ@S-nZVI进行综合表征分析。考察投加量、初始pH以及共存离子等因素对HJ@S-nZVI去除磷酸盐效果的影响,并结合吸附等温线和吸附动力学研究其吸附性能和吸附机理。结果表明：HJ@S-nZVI的优化制备条件为铁负载比为0.25,S/Fe为0.01,陈化时间为10 d;SEM、EDS和元素分布图分析表明,硫化零价铁以球状颗粒形式成功负载于杭锦土表面,XPS表明HJ@S-nZVI表面铁的主要存在形态为FeS和FeOOH等;投加量、初始pH和SiO₃ ²⁻共存对HJ@S-nZVI去除磷酸盐的效果影响较大,而SO₄ ²⁻、CO₃ ²⁻和Cl⁻共存对磷酸盐的去除效果无明显竞争影响;HJ@S-nZVI对磷酸盐的吸附过程符合Freundlich等温模型（R²=0.992）,不同初始浓度下,准二级动力学模型可较好地描述磷酸盐的去除过程（R²>0.995）。     

The colorful chemistry of nanoscale zero-valent iron (nZVI)

正Nanoscale zero-valent iron(nZVI)possesses unique chemistry and capability for the separation and transformation of a growing number of environmental contaminants.A n ZVI particle consists of two nanoscale components,an iron(oxyhydr)oxides shell and a metallic iron core.This classical"core-shell"structure offers n ZVI with unique and multifaceted     

纳米零价铁及其双金属体系对菲的降解研究

以实验室合成的纳米零价铁(n ZVI)及其双金属(n ZVI/Cu和n ZVI/Ni)为反应材料,对菲(Phenanthrene)的去除进行研究.表征结果表明:纳米颗粒平均粒径均为80~100 nm,主要以α-Fe0的形式存在.批实验结果表明,5 g·L-1的n ZVI,n ZVI/Cu和n ZVI/Ni对菲溶液均有去除效果,其去除效率依次为n ZVI/Nin ZVI/Cun ZVI.溶液初始p H为7.5时,5 g·L-1的n ZVI/Ni去除88%0.5 mg·L-1的菲只需3 h,而n ZVI/Cu和n ZVI分别需要29 h和40 h.3种纳米铁对菲的去除率均随着n ZVI投加量的增加而升高,随着菲溶液初始浓度的增加而降低.反应温度的升高可提高n ZVI/Ni对菲的去除效率,高温时(≥30℃)菲的降解遵循一级反应动力学模型.p H对反应影响不大.GC-MS结果表明,n ZVI/Ni降解菲溶液主要为催化加氢反应,而n ZVI/Cu和n ZVI对菲溶液的去除主要为吸附作用.     

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron: High resolution chemical mapping of the passivation layer

Solid phase reactions of Cr(Ⅵ) with Fe(0) were investigated with spherical-aberration-corrected scanning transmission electron microscopy(Cs-STEM) integrated with X-ray energy-dispersive spectroscopy(XEDS). Near-atomic resolution elemental mappings of Cr(Ⅵ)–Fe(0) reactions were acquired. Experimental results show that rate and extent of Cr(Ⅵ) encapsulation are strongly dependent on the initial concentration of Cr(Ⅵ) in solution. Low Cr loading in nZⅥ(1.0 wt%) promotes the electrochemical oxidation and continuous corrosion of n ZⅥ while high Cr loading(1.0 wt%) can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr(Ⅵ)(e.g., 10 mg/L). Whereas the reacted n ZⅥ is quickly coated with a newly-formed layer of 2–4 nm in the presence of concentrated Cr(Ⅵ)(e.g., 100 mg/L). The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy(XPS) depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxides with Cr(Ⅵ) adsorbed on the outside surface. The insoluble and insulating Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxide layer can completely cover the n ZⅥ surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZⅥ in high Cr(Ⅵ) solution is detrimental to the performance of nZⅥ for Cr(Ⅵ) treatment and remediation.     

有机膨润土负载纳米铁去除废水中硝基苯

用具有良好吸附能力的有机膨润土作载体,通过FeSO4与NaBH4反应制得负载型的纳米铁(NZVL/CTMAB-Bent),用XRD、BET对其性能进行了表征.以硝基苯为目标污染物,试验了 -NZVI/CTMAB-Bent对不同起始浓度硝基苯的去除作用,考察了介质PH对其去除效率的影响,并与相同铁含量的纳米铁(NZVI)进行了比较.此外.还对NZVI/CTMAB-Bent还原硝基苯的机理进行了探讨.结果表明,NZVI/CTMAB-Bent对硝基苯的去除能力远高于相同铁含量的NZVI.也明显优于相同含量的有机膨润土和相同铁含量的NZVI对硝基苯去除率的加和.     

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%.     

双表面活性剂修饰下纳米零价铁对水中Cr(Ⅵ)污染去除研究

为解决纳米级零价铁（nZVI）在环境中易团聚、易氧化的问题,强化其去除水中Cr（VI）的能力,选择非离子型表面活性剂聚乙烯吡咯烷酮（PVP）和阴离子表面活性剂油酸钠（NaOA）同时对nZVI进行修饰.同时,通过对比不同pH值、材料干湿状态、初始浓度及共存离子条件下的反应效果,结合材料的XRD和XPS表征、动力学实验和25℃等温线的拟合进行机理分析.结果表明：酸性条件有利于Cr（VI）的去除;材料的干湿状态对去除效率影响较大;材料去除水中Cr（VI）可在3 h内达到反应平衡,去除效率在90%以上,实验条件下最大去除量为183.1 mg·g^-1,反应过程符合准二级动力学模型及Langmuir模型;反应过程中Cr（VI）大部分转化为Cr（Ⅲ）.     

Humic acid and metal ions accelerating the dechlorination of 4-chlorobiphenyl by nanoscale zero-valent iron

Transformation of polychlorinated biphenyls (PCBs) by zero-valent iron represents one of the latest innovative technologies for environmental remediation. The dechlorination of 4-chlorobiphenyl (4-ClBP) by nanoscale zero-valent iron (NZVI) in the presence of humic acid or metal ions was investigated. The results showed that the dechlorination of 4-ClBP by NZVI increased with decreased solution pH. When the initial pH value was 4.0, 5.5, 6.8, and 9.0, the dechlorination efficiencies of 4-ClBP after 48 hr were 53.8%, 47.8%, 35.7%, and 35.6%, respectively. The presence of humic acid inhibited the reduction of 4-ClBP in the first 4 hr, and then significantly accelerated the dechlorination by reaching 86.3% in 48 hr. Divalent metal ions, Co2+, Cu2+, and Ni2+, were reduced and formed bimetals with NZVI, thereby enhanced the dechlorination of 4-ClBP. The dechlorination percentages of 4-ClBP in the presence of 0.1 mmol/L Co2+, Cu2+ and Ni2+ were 66.1%, 66.0% and 64.6% in 48 hr, and then increased to 67.9%, 71.3% and 73.5%, after 96 hr respectively. The dechlorination kinetics of 4-ClBP by the NZVI in all cases followed pseudo-first order model. The results provide a basis for better understanding of the dechlorination mechanisms of PCBs in real environment.     

改性生物炭负载纳米零价铁活化过硫酸盐降解活性蓝19的机理及老化研究

采用磷酸改性的黍糠基生物炭作为纳米零价铁(Nanoscale zero-valent iron,nZVI)载体,成功制备出一种高效非均相活化材料一磷酸改性生物炭负载纳米零价铁(nZVI@PBC),用来活化过硫酸盐(Persulfate,PS)降解印染废水中的典型染料—活性蓝(Reactive Blue 19,RB19)...     

海藻酸钠/蒙脱石联合负载型纳米Fe0对Cu(II)的去除研究

由于蒙脱石负载型纳米Fe~0(Mt-n ZVI)在使用中易随水迁移,造成出水水质混浊和Fe~0流失.因此,本研究制备了海藻酸钠(SA)和蒙脱石(Mt)联合负载型纳米零价铁(SA/Mt-n ZVI),探究其对水中Cu(Ⅱ)的去除效果,并考察了Cu(Ⅱ)初始浓度、pH值对去除率的影响.结果表明:以2%(质量分数)SA和6%(质量分数)Mt-n ZVI条件制备的SA/Mt-n ZVI小球对Cu(Ⅱ)处理效果好,反应24 h后,SA/Mt-n ZVI小球对初始浓度为40 mg·L-1Cu(Ⅱ)的去除率达到92.11%,与游离的Mt-n ZVI颗粒相比,其活性并未降低;Cu(Ⅱ)的去除率随其初始浓度升高而降低;在pH为2~6之间,Cu(Ⅱ)去除率随pH升高而升高.SA/Mt-n ZVI小球可有效净化污水中的Cu(Ⅱ),将其重复使用3次后,对Cu(Ⅱ)的去除率仍维持在59.52%.     

微米零价铁去除磷酸盐效果与机理研究

为探究微米零价铁除磷效果与机理,首先考察了水化学条件对微米零价铁除磷效果的影响;其次研究了微米零价铁对磷的去除效果以及酸盐磷在磁性固体和悬浮固体中的动态分配情况,并通过监测不同浓度反应体系中理化参数(pH、DO、ORP)的变化,进一步分析了体系中的反应过程;最后通过扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等表征手段对反应产物进行了分析。结果表明:较低pH能显著提高微米零价铁的反应活性,加快磷的去除;离子强度的增加可加快反应速率; AsO 4 3 -和 SiO 3 2 -对微米零价铁除磷具有明显的抑制作用, SO 4 2 -影响很小,而 NO 3 -和 CO 3 2 -有一定的促进作用。被去除的磷酸盐在反应产物磁性固体和悬浮固体中的浓度接近。SEM分析表明,有磷条件与无磷条件下反应产物固体表面形貌具有明显区别。XPS分析表明,微米零价铁除磷过程中主要生成了Fe2+铁和Fe3+。1,10-菲啰啉掩蔽试验结果表明,磷酸盐与Fe2+结合是微米零价铁除磷的主要途径。XRD分析发现生成了H2FeP2O7,说明微米零价铁除磷存在沉淀作用。     

改性生物炭负载nZVI对土壤Cr(VI)的修复差异研究

考察了生物炭(BC)、酸洗生物炭(HCl-BC)和纳米零价铁负载生物炭(n ZVI-HCl-BC)对土壤中Cr(VI)还原和总Cr形态转化的影响.结果表明,生物炭对Cr(VI)还原率随土壤含水率的升高而显著提高.在较高土壤含水率(70%)条件下,各生物炭对Cr(VI)的最高还原率排序为:HCl-BC(97.26%)n ZVI-HCl-BC(88.36%)BC(87.61%).在不同Cr(VI)污染水平下(150、300、600和900 mg·kg~(-1)),HCl-BC对土壤中Cr(VI)的还原率最高.随Cr(VI)含量升高,BC和HCl-BC对Cr(VI)的还原率呈降低趋势,而n ZVI-HCl-BC对Cr(VI)的还原率为先降低后升高.形态分析表明,生物炭在不同程度上增加了土壤中Cr残渣态的比例:n ZVI-HCl-BC(11.58%)HCl-BC(9.53%)BC(1.42%),表明生物炭对土壤Cr起到稳定作用.综上,改性生物炭显著促进Cr(VI)还原及总Cr向残渣态转化,表明其具有修复Cr污染土壤的潜力.     

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.     

维生素B12催化纳米零价铁仿生降解全氟辛磺酸

研究了维生素B₁₂（VB₁₂）催化纳米零价铁（nFe⁰）仿生还原降解工业级全氟辛磺酸（PFOS）.结果表明,VB₁₂催化nFe⁰不仅能够降解支链PFOS,而且也能够同时降解直链PFOS,这是首次报道直链PFOS的仿生还原降解.PFOS降解过程可用准一级动力学模型模拟,且升高温度有利于PFOS的还原降解去除和脱氟.超高效液相色谱-四级杆飞行时间质谱（UPLC-QTOF）定性分析表明,PFOS仿生降解产物包括4种全氟磺酸类（全氟碳链长度为C4~C7）、9种全氟羧酸类（全氟碳链长度为C2~C7、C10、C11和C13）和5种多氟代酸类（即H-全氟己酸、H-全氟庚酸、H-全氟辛酸、H₂-全氟辛酸和H-全氟辛磺酸）化合物.全氟磺酸类和全氟羧酸类化合物首次在VB₁₂仿生催化降解PFOS的产物之中检出,其中全氟十一烷酸（C10）、全氟十二烷酸（C11）和全氟十四烷酸（C13）等长链化合物第一次在降解PFOS过程中被发现.在降解样中检出的H-全氟烷烃（链长为C2~C7、C10、C11和C13）是否是PFOS的仿生降解产物,还有待进一步研究确认.     

维生素B12催化纳米零价铁仿生降解全氟辛磺酸

研究了维生素B₁₂（VB₁₂）催化纳米零价铁（nFe⁰）仿生还原降解工业级全氟辛磺酸（PFOS）.结果表明,VB₁₂催化nFe⁰不仅能够降解支链PFOS,而且也能够同时降解直链PFOS,这是首次报道直链PFOS的仿生还原降解.PFOS降解过程可用准一级动力学模型模拟,且升高温度有利于PFOS的还原降解去除和脱氟.超高效液相色谱-四级杆飞行时间质谱（UPLC-QTOF）定性分析表明,PFOS仿生降解产物包括4种全氟磺酸类（全氟碳链长度为C4~C7）、9种全氟羧酸类（全氟碳链长度为C2~C7、C10、C11和C13）和5种多氟代酸类（即H-全氟己酸、H-全氟庚酸、H-全氟辛酸、H₂-全氟辛酸和H-全氟辛磺酸）化合物.全氟磺酸类和全氟羧酸类化合物首次在VB₁₂仿生催化降解PFOS的产物之中检出,其中全氟十一烷酸（C10）、全氟十二烷酸（C11）和全氟十四烷酸（C13）等长链化合物第一次在降解PFOS过程中被发现.在降解样中检出的H-全氟烷烃（链长为C2~C7、C10、C11和C13）是否是PFOS的仿生降解产物,还有待进一步研究确认.