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.     

Removal of Cr(VI) from simulative contaminated groundwater by iron metal

The Cr(VI) removal from simulative contaminated groundwater using zero-valent iron (Fe⁰) filings, Fe⁰ powder and nanoscale Fe⁰ in batch experimental mode was studied. Cr(VI) is a primary pollutant of some soils and groundwater. Zero-valent iron, an important natural reductant, could transform Cr(VI) to Cr(III) which is much less toxic and immobile. The Cr(VI) removal percentage was 87% at a metal to solution ratio of 6 g l⁻¹ for commercial iron powder (200 mesh) in 120 min, and 100% Cr(VI) was removed when the metal to solution ratio was 10 g l⁻¹. The results demonstrates that the Cr(VI) removal percentage was affected apparently by pH, the amount of Fe powder and the reaction temperature. The Cr(VI) removal percentage with nanoscale Fe⁰ was much higher than those with Fe⁰ filings or Fe⁰ powder at the same reaction time. Electrochemical analysis of the reaction process led to the conclusion that the Cr(VI) trended to form Cr(III) hydroxide under the reaction conditions. The kinetics analysis showed that Cr(VI) reduction by Fe⁰ could be described as a pseudo-first-order kinetics model.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.     

“混凝沉淀+纳米零价铁”处理印刷电路板生产废水中试研究

提出一种新纳米零价铁反应器(Nanoscale Zero-Valent Iron Reactor,简称NIR)及"混凝沉淀+纳米零价铁"处理工艺,通过实际生产废水进行中试,考察和研究该工艺和NIR技术处理江苏省某市印刷电路板(Printed Circuit Board,简称PCB)工业园区废水的效果。结果表明,此工艺对PCB生产废水中Cu、TP及COD Cr去除率分别可达到97.3%、73.7%、26%,其中Cu处理效果最佳;XRD结果表明,纳米零价铁(Nanoscale Zero-Valent Iron,nZVI)与PCB生产废水反应后含有γ-Fe2O3、Fe3O4、γ-FeOOH、CuO、Cu2O、Cu0等产物。"混凝沉淀+纳米零价铁"工艺处理废水时具有处理效果好、工艺耐冲击性能好、产泥量小、不易造成二次污染等优点。     

纳米零价铁在应用中存在的问题及提高反应活性的方法

纳米零价铁对多种污染物质均有较好的去除效果,在污染的水体、土壤及底泥中被广泛研究与应用。前人对纳米零价铁的制备、在污染治理各方面的应用、作用的机理等方面进行了较为详细的总结,针对纳米零价铁在应用中存在的问题虽有提及,但少有人集中进行整理。本文主要针对纳米零价铁在环境治理方面存在的问题进行论述并对提高其反应活性的常用方法进行了总结,以期为纳米零价铁实际应用领域的深入研究提供借鉴并拓展新的思路。     

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.      

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.     

Effects of suspended common-scale and nanoscale particles on the survival,growth and reproduction of Daphnia magna

Suspended particles are a natural component of aquatic ecosystems. This study provides a report on the survival, growth and reproduction of common-scale and nanoscale particles of Daphnia magna Straus exposed to five types of particles (i.e. KN (kaolinite), MN (montmorillonite), MNn (nanoscale MN), NP (natural particles), and NPn (nanoscale NP)). The results of the study show that the suspended particles elicited a dose-dependent toxicity in KN, MN and MNn, with the following toxicity pattern: MN > KN > MNn. On the contrary, NP and NPn did not show any harmful effects on the animals. Instead, NP and NPn, especially NPn, contributed to the survivorship of the animals. The animals were able to survive throughout the 21-day period of bioassays, and when the particle concentration reached 600 mg L⁻¹, they produced many neonates without any addition of food. This experimental results also indicated that the nanoscale particles were less toxic than the common-scale ones, both for MN and NP. Moreover, the results of the 21-day period of bioassays indicated that when the organisms were exposed to particles of different size scales, they showed different selection patterns for allocating resources. This may be due to the generation of different assimilation and digestion patterns.