不同pH条件下赤铁矿纳米粒子的聚集和再分散行为研究

纳米粒子的聚集和再分散行为是影响纳米粒子在环境中归趋的重要因素.选取赤铁矿纳米粒子作为研究对象,用Zeta电位和粒径测定仪系统研究其在不同pH条件下的聚集和再分散过程.结果表明,当pH在7.0～8.7之间时,赤铁矿纳米粒子发生较快的聚集(如当pH为8.2时平均粒径在400s内由31nm增加到1400nm).当pH≤6.3时,赤铁矿纳米粒子几乎不发生聚集.不经老化聚集的赤铁矿纳米粒子均能发生再分散,但是再分散过程并不完全可逆,而是呈现一定的非线性.老化使得更多的赤铁矿纳米粒子发生不可逆的聚集,在等电点处老化后的样品不发生再分散.当pH为7.0和8.9时,老化的样品再分散后的平均粒径(约500nm)大于不老化的样品(约250nm).纳米粒子聚集-再分散过程的非线性对预测其在环境中的存在状态和生态效应带来了大的困难.     

Stabilization of Fe0 nanoparticles with silica fume for enhanced transport and remediation of hexavalent chromium in water and soil

Effective in situ remediation of Cr(VI) in groundwater requires the successful delivery of reactive iron particles to the subsurface. Fe0 nanoparticles (20–110 nm diameter) supported on silica fume were synthesized by borohydride reduction of an aqueous iron salt in the presence of a support material. The experimental result showed that attachment of Fe0 nanoparticles on the commercial available sub-micrometer silica fume prevented them from aggregation while maintaining the particle reactivity. When the Fe0 concentration was 0.4 g/L, 88.00% of 40 mg/L Cr(VI) was removed by silica fume-supported Fe0 nanoparticles (SF-Fe0) in 120 min, 22.55% higher than unsupported Fe0. Furthermore, transport experiments confirmed that almost all unsupported Fe0 was retained, whereas 51.50% and 38.29% of SF-Fe0 were eluted from the vertical and horizontal sand column, respectively. Additionally, the effect of solution ionic strength on the transport ability of SF-Fe0 was evaluated. The result showed that increase in the salt concentration led to a decrease in the mobility and also the divalent ion Ca2+ had a greater effect than that of monovalent ion Na+.     

纳米银毒理学研究进展

纳米银因其优越的抗菌性能被广泛应用于环境、农业、医药等领域。以往的研究从体内试验和体外试验方面对纳米银的健康影响及其作用机制进行了探讨,然而,由于研究设计或研究条件等方面的限制,以往的研究结果仍存在一些不足,迄今为止,有关纳米银对健康的影响及其作用机制仍不很清楚。综述了近年来在纳米银毒理学研究方面所取得的进展以及目前研究中的不足,并展望了未来研究的方向。     

绿色合成纳米铁同时去除水体中的Pb(Ⅱ)和Cd(Ⅱ)

植物提取液绿色合成纳米铁是用于环境修复最有潜力的技术之一.本文利用苦丁茶提取液绿色合成纳米铁(Fe NPs),考察了Fe NPs去除Pb(Ⅱ)和Cd(Ⅱ)的性能,同时,比较了不同温度对Fe NPs去除Pb(Ⅱ)和Cd(Ⅱ)的影响.结果表明,在p H=3.5、温度303 K、Fe NPs投加量为2.0 g·L-1的条件下,反应60 min后,Pb(Ⅱ)和Cd(Ⅱ)复合溶液中Pb(Ⅱ)的去除率为91.0%,Cd(Ⅱ)的去除率达31.4%,而单独的Pb(Ⅱ)和Cd(Ⅱ)溶液中,Pb(Ⅱ)的去除率高达93.8%,Cd(Ⅱ)的去除率高达41.7%.根据Fe NPs对Pb(Ⅱ)和Cd(Ⅱ)反应前后的表征结果和Pb(Ⅱ)和Cd(Ⅱ)去除动力学的研究结果表明,Pb(Ⅱ)的去除反应遵循伪一级动力学,而Cd(Ⅱ)的去除遵循伪二级动力学,去除机理可能是Fe NPs对Pb(Ⅱ)起到还原、吸附作用,而对混合液中的Cd(Ⅱ)起到吸附作用.     

离子型表面活性剂改性绿色合成单分散纳米氧化铁的制备及其吸附磷的性能

由于绿色合成单分散纳米氧化铁(IONP)易团聚,本研究分别利用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和阴离子表面活性剂十二烷基硫酸钠(SDS)作为分散剂和稳定剂改善单分散纳米氧化铁的性能从而提高其对水体中磷的吸附.在磷酸根初始浓度20 mg·L-1,反应温度25℃的条件下,CTAB-IONP对磷酸根的去除率为92.47%,IONP对磷酸根的去除率为81.94%,SDS-IONP对磷的吸附率略微降低至79.38%.SEM表明IONP、CTAB-IONP,SDS-IONP的平均粒径依次约为180、90、60 nm.同时,EDS、UV-vis、FTIR和Zeta电位的结果说明这些表面活性剂改善了单分散纳米氧化铁的粒径,提高其分散度,改变其表面带电情况.此外,动力学结果均符合伪二级吸附动力学(R20.9).最后,表面活性剂具有调控绿色合成单分散纳米氧化铁活性的潜能,是绿色合成在原位环境修复中新的亮点.     

Preparation and characterization of Pd/Fe bimetallic nanoparticles immobilized on Al2O3/PVDF membrane: Parameter optimization and dechlorination of dichloroacetic acid

Using a liquid–solid phase inversion method, a hybrid matrix poly(vinylidene fluoride)(PVDF) membrane was prepared with alumina(Al2O3) nanoparticle addition. Pd/Fe nanoparticles(NPs) were successfully immobilized on the Al2O3/PVDF membrane, which was characterized by Scanning Electron Microscopy(SEM) and Transmission Electron Microscopy(TEM). The micrographs showed that the Pd/Fe NPs were dispersed homogeneously. Several important experimental parameters were optimized, including the mechanical properties, contact angle and surface area of Al2O3/PVDF composite membranes with different Al2O3 contents. At the same time, the ferrous ion concentration and the effect of hydrophilization were studied. The results showed that the modified Al2O3/PVDF membrane functioned well as a support. The Al2O3/PVDF membrane with immobilized Pd/Fe NPs exhibited high efficiency in terms of dichloroacetic acid(DCAA) dechlorination. Additionally, a reaction pathway for DCAA dechlorination by Pd/Fe NPs immobilized on the Al2O3/PVDF membrane system was proposed.     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

鲤鱼对纳米二氧化钛的生物富集

建立了浓硫酸-硫酸铵酸化消解-ICP测定水样及鱼样中纳米二氧化钛的方法,并研究了纳米二氧化钛在鲤鱼(Cyprinus carpio)体内的富集.酸化消解-ICP测定方法对20.0 mg/L纳米二氧化钛水样,测定的相对标准偏差仅为4.53%.纳米二氧化钛在水样和鱼样中的加标回收率分别为94%～104%和90%～103%,可以精确测定环境样品中纳米二氧化钛浓度.纳米二氧化钛在鱼体内有较高的富集,暴露于3 mg/L、10 mg/L纳米二氧化钛悬浮液的鲤鱼,25 d时鱼体内的二氧化钛浓度分别达到2.1 mg/g和5.8 mg/g.达到平衡时,BCF分别为675.5和595.4.纳米二氧化钛在鱼鳃、内脏中有很大程度的富集,肌肉部分对纳米二氧化钛的富集最少.