Effects of ionic strength and temperature on the aggregation and deposition of multi-walled carbon nanotubes

The aggregation and deposition of carbon nanotubes(CNTs) determines their transport and fate in natural waters.Therefore,the aggregation kinetics of humic-acid treated multi-walled carbon nanotubes(HA-MWCNTs) was investigated by time-resolved dynamic light scattering in NaCl and CaCl_2 electrolyte solutions.Increased ionic strength induced HA-MWCNT aggregation due to the less negative zeta potential and the reduced electrostatic repulsion.The critical coagulation concentration(CCC) values of HA-MWCNTs were 80 mmol/L in NaCl and 1.3 mmol/L in CaCl_2 electrolyte,showing that Ca~(2+) causes more serious aggregation than Na~+.The aggregation behavior of HA-MWCNTs was consistent with Derjaguin-Landau-Verwey-Overbeek theory.The deposition kinetics of HA-MWCNTs was measured by the optical absorbance at 800 ran.The critical deposition concentrations for HA-MWCNT in NaCl and CaCl_2 solutions were close to the CCC values,therefore the rate of deposition cannot be increased by changing the ionic strength in the diffusion-limited aggregation regime.The deposition process was correlated to the aggregation since larger aggregates increased gravitational deposition and decreased random Brownian diffusion.HA-MWCNTs hydrodynamic diameters were evaluated at 5,15 and 25℃.Higher temperature caused faster aggregation due to the reduced electrostatic repulsion and increased random Brownian motion and collision frequency.HA-MWCNTs aggregate faster at higher temperature in either NaCl or CaCl_2electrolyte due to the decreased electrostatic repulsion and increased random Brownian motion.Our results suggest that CNT aggregation and deposition are two correlated processes governed by the electrolyte,and CNT transport is favored at low ionic strength and low temperature.     

天然有机质模型化合物分子结构对碳纳米管分散性的影响

研究了不同分子结构的天然有机物质（NOM）模型化合物单宁酸（TA）、没食子酸（GA）和十二烷基苯磺酸钠（SDBS）对碳纳米管（CNTs）分散性的影响.通过计算得出,TA的临界胶束浓度（CMC）为1.12mmol/L,SDBS的CMC为0.24mmol/L,GA在所测试的浓度范围内没有形成胶束.比较NOM在CNTs表面的吸附过程和CNTs的分散过程,表明空间位阻和胶束包裹是2个促进CNTs分散的主要机理.借助透射电子显微镜（TEM）和测量悬浮的CNTs的平均流体动力学直径（DLS）结果表明,TA在较少的固相吸附量（S_e ≈ 0.01mmol/g）就能使CNTs分散,归因于其吸附后刚性芳香三维结构的TA能形成的较大空间位阻;同样具有芳香平面结构的GA分子在CNTs表面的吸附需要达到一定的厚度（S_e > 0.2mmol/g）,才能有效地分散CNTs;具有烷基脂肪链的SDBS,需要在形成半胶束或胶束后（S_e > 0.13mmol/g） CNTs才能有效地被分散.芳香族刚性结构和脂肪族柔性结构的模型化合物对CNTs的分散效果和机理存在较大的差别.     

Adsorption of atrazine by natural organic matter and surfactant dispersed carbon nanotubes

The aggregation and dispersion behaviors of carbon nanotubes (CNTs) can regulate the environmental spread and fate of CNTs, as well as the organic pollutants adsorbed onto them. In this study, multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) were surface modified with humic acids from di erent sources and with surfactants of di erent ionic types. The dispersion stability of surface modified CNTs was observed by UV-Vis spectrophotometry. The e ect of humic acid and surfactant dispersion on the adsorption of atrazine by CNTs was investigated by batch equilibrium experiments. Both humic acid and surfactant could e ectively disperse MWNTs, but not SWNTs, into stable suspensions under the studied conditions. Surface modified CNTs had a greatly reduced capacity for adsorption of atrazine. The inhibitory e ect of peat humic acid was relatively stronger than that of soil humic acid, but the two surfactants had a similar inhibitory e ect on atrazine adsorption by the two CNT types. Increases in surfactant concentration resulted in rapid decreases in the adsorption of atrazine by CNTs when the surfactant concentration was less than 0.5 critical micelle concentration.     

Application potential of carbon nanotubes in water treatment：A review

Water treatment is the key to coping with the conflict between people’s increasing demand for water and the world-wide water shortage. Owing to their unique and tunable structural, physical, and chemical properties, carbon nanotubes (CNTs) have exhibited great potentials in water treatment. This review makes an attempt to provide an overview of potential solutions to various environmental challenges by using CNTs as adsorbents, catalysts or catalyst support, membranes, and electrodes. The merits of incorporating CNT to conventional water-treatment material are emphasized, and the remaining challenges are discussed.     

碳纳米管基复合吸附剂的制备及其吸附性能

为了解决碳纳米管(CNTs)在吸附水中污染物时易聚集、难分离的问题,本文采用静电自组装技术将碳纳米管固定化在具有微米级粒径的碳酸钙颗粒表面,设计制备了壳-核结构的CNTs基复合吸附剂.实验考查了不同碳纳米管分散体系对复合吸附剂制备的影响,并采用Zeta电位、拉曼光谱、扫描电镜等手段对复合吸附剂的制备过程和结构进行表征,探讨了制备的碳纳米管基复合吸附剂对菲的吸附性能.结果发现,复合吸附剂对菲的吸附能力随CNTs载量的增加而增大,CNTs标化的吸附系数则随CNTs载量的增加而下降,碳纳米管是复合吸附剂的主要吸附位点.     

多壁碳纳米管分阶段暴露对热带爪蛙胚胎发育的毒性

近年来,碳纳米管（CNTs）的产量和使用量不断增大,提高了其释放到环境中的可能性.尽管碳纳米管的水生生态毒性有所报道,但对两栖动物胚胎的发育毒性研究仍比较少.本研究采用分阶段暴露的方式,以热带爪蛙胚胎的死亡率、孵化率、畸形率、畸形类型、心率、体长等作为毒性评价指标,研究不同浓度多壁碳纳米管（25、50 mg·L^-1）对爪蛙胚胎发育的胚胎毒性与敏感窗口.结果显示,多壁碳纳米管可导致爪蛙胚胎死亡率升高,孵化率降低,但对其心率、体长没有显著性影响（p>0.05）.产生的畸形类型包括心腔水肿、脊索弯曲、泄殖腔畸形、眼睛畸形等,其中,心腔水肿占的比例最大为28.7%.另外,根据死亡率、孵化率、畸形率等指标综合评价爪蛙胚胎对多壁碳纳米管的敏感程度,由强到弱的顺序依次是：原肠胚期、囊胚期、神经胚期、尾芽期.研究表明,浓度为25 mg·L^-1和50 mg·L^-1的多壁碳纳米管对热带爪蛙胚胎发育具有一定的毒性作用,其作用机理与胚胎卵膜粘附碳纳米管有间接关系,研究结果可为合理评价碳纳米管对水生生物胚胎的影响提供一定的理论参考.     

Novel Al-doped carbon nanotubes with adsorption and coagulation promotion for organic pollutant removal

Al-doped carbon nanotubes (Al-doped CNTs) were prepared as a multifunctional integrated material of adsorbent and coagulant aid for organic pollutant removal from aqueous solution. It was observed that aluminum species were dispersed homogeneously on the surface of CNTs, and mainly anchored onto defect structures of the CNTs. The introduction of aluminium efficiently improved adsorption ability for methyl orange (MO) onto the CNTs, and maximum adsorption capacity calculated from the Langmuir isotherm model can reach 69.7 mg/g. The MO adsorption kinetics can be better described by the pseudo-second-order and pore diffusion kinetic models, and the diffusion of MO anions into pores of the Al-doped CNT adsorbent should be the rate-determining step. Thermodynamic analyses indicated that the adsorption of MO onto Al-CNTs-2.0 was endothermic and spontaneous. Moreover, adsorption capacity for MO on the Al-doped CNTs was evidently dependent on the CNT dose, solution pH and adsorbent dose. From the perspective of low-cost and multifunctional, suspension obtained during the Al-doped CNT adsorbent preparation, was tested as coagulant to remove humic acid (HA). A significant observation is that the suspension exhibited an excellent coagulation performance for HA, because abundant aluminous polymer and Al-doped CNTs existed in the suspension.     

天然水体中多壁纳米碳管对纳米氧化锌颗粒团聚与沉降行为的影响

研究了淡水湖泊水体中氧化多壁纳米碳管(Oxidized-multiwalled carbon nanotubes,o-MWCNTs)对纳米氧化锌(ZnO nanoparticles,nZnO)颗粒团聚与沉降行为的影响,探讨了天然胶体及o-MWCNTs的浓度对nZnO颗粒团聚粒径、团聚速率及沉降行为的作用.结果表明,nZnO在天然水体中会发生明显沉降,相比去除天然胶体的天然水而言,天然胶体的存在显著减少了nZnO的沉降.这主要归因于nZnO-天然胶体颗粒间的作用能垒高于nZnO-nZnO颗粒间的作用能垒,使得天然胶体的存在降低了nZnO-nZnO之间的颗粒碰撞效率,从而促进nZnO悬浮.o-MWCNTs对nZnO在天然水体中沉降行为的影响与天然胶体密切相关.相比于nZnO的单独沉降,在不过膜天然水中(含天然胶体),低浓度o-MWCNTs的存在增加了颗粒间的团聚速率,从而促进nZnO的沉降,而高浓度o-MWCNTs降低了颗粒间的团聚速率和团聚体粒径,从而降低了nZnO的沉降.而在过膜天然水中(不含天然胶体),o-MWCNTs的存在显著降低了颗粒间的团聚粒径和团聚速率,从而降低了nZnO的沉降,且o-MWCNTs的浓度越高,对nZnO悬浮稳定性的促进作用越明显.     

腐殖酸对水中多壁碳纳米管凝聚特性的影响

以多壁碳纳米管(MWNTs)稳定悬浮液为对象,研究了腐殖酸(HA)对水中MWNTs凝聚特性的影响.结果表明,采用SDS超声分散法制备的MWNTs稳定悬浮液具有较强的稳定性,投加电解质可通过压缩双电层机制使其发生凝聚,并符合经典的DLVO理论.HA存在时,可通过增大MWNTs颗粒间的空间位阻效应和亲水性,抑制凝聚反应发生,从而提高其在水中的稳定性.Ca2+可与HA发生络合桥联作用,导致MWNTs颗粒粒径的大幅提高,强化凝聚发生.水中MWNTs的分散和凝聚性质将受到有机物性质和电解质种类等复杂因素的影响.     

Removal of dispersant-stabilized carbon nanotubes by regular coagulants

Coagulation followed by sedimentation, as a conventional technique in the water treatment plant, can be the first line of defense against exposures of carbon nanotubes (CNTs) to aquatic organisms and human beings, which has been rarely documented. This study investigated the removal of dispersant-stabilized CNT suspensions by poly aluminum chloride (PACl) and KAl(SO₄)₂. 12H₂O (alum), with a focus on the effects of dispersant type, coagulant type and dosage. PACl performed better than alum in the removal of tannic acid-, humic acid-, and sodium dodecyl benzenesulfonate-stabilized CNTs, but worse for polyethylene glycol octylphenyl ether (TX100)-stabilized CNTs. Neither coagulant could effectively precipitate cetyltrimethyl ammonium bromide-stabilized CNTs. The removal by PACl first increased up to a plateau and then decreased with the continued increase of coagulant dosage. However, the removal rates leveled off but did not decrease after achieving their highest level with the continued addition of alum. The coagulation and flocculation of the CNT suspensions by PACl could be regulated mainly by the mechanism of adsorption charge neutralization, whereas the coagulation by alum mainly involved electrical double-layer compression.     

Influences of perfluorooctanoic acid on the aggregation of multi-walled carbon nanotubes

The aggregation of multi-walled carbon nanotubes (MWCNTs) in the aqueous phase not only inhibits their extensive utilization in various aspects but also dominates their environmental fate and transport.The role of surfactants at low concentration in the aggregation of MWCNTs has been studied,however the effect of perfluorinated surfactants at low concentration is uncertain.To understand this interfacial phenomenon,the influences of perfluorooctanoic acid (PFOA),and sodium dodecyl sulfate (SDS) as a control,on MWCNT aggregation in the aqueous phase were examined by the UV absorbency method.Influences of pH and cationic species on the critical coagulation concentration (CCC) value were evaluated.The CCC values were dependent on the concentration of PFOA,however a pronounced effect of SDS concentration on the CCC values was not observed.The CCC values of the MWCNTs were 51.6 mmol/L in NaCl and 0.28 mmol/L in CaCl 2 solutions,which suggested pronounced differences in the effects of Na+ and Ca2+ ions on the aggregation of the MWCNTs.The presence of both PFOA and SDS significantly decreased the CCC values of the MWCNTs in NaCl solution.The aggregation of the MWCNTs took place under acidic conditions and was not notably altered under neutral and alkaline conditions due to the electrostatic repulsion of deprotonated functional groups on the surface of the MWCNTs.     

不同分散条件和pH值对TiO_2悬浊液性能影响研究

TiO2悬浊液的稳定性对于光催化应用而言是非常重要的。对于不同粒径的纳米TiO2颗粒在超声分散和搅拌分散、不同pH条件下的团聚和沉降进行了考察,结果显示颗粒的团聚和沉降与分散形式、颗粒粒径、pH值密切相关。颗粒采用超声分散的稳定性较好,但仍会发生沉降,而颗粒粒径越大,团聚和沉降越明显;pH值的影响与距离等电点远近有关系,越近则越容易团聚和沉降,但酸性条件下的分散性要好于碱性条件。结合相关理论,对于其中的机理也进行了探讨。     

泥沙沉降对水体中溶解性有机物光谱学特性的影响

以沈阳市新开河为研究对象,考察了泥沙沉降过程中,沉降时间、泥沙含量、pH、盐度对水体中溶解性有机物(DOM)的含量和光谱学特性的影响.结果表明,泥沙沉降条件下,水体中DOC随泥沙沉降时间的增长而先增大后减小,随泥沙含量的增加而先减小后增大,随pH的增大而增大,随盐度的增大而减小.随着pH的增大,水体中DOM的芳香性增强;随着盐度的增大,水体中DOM的芳香性降低.随着泥沙沉降时间的增长,DOM中各类荧光物质的含量先增加后减少;随着泥沙含量的增加,DOM中类腐殖酸和类富里酸荧光物质的含量增加,而类溶解性微生物代谢产物荧光物质和类芳香族蛋白质荧光物质的含量降低.在泥沙沉降过程中,下层水体中DOC、在波长为254 nm处的紫外吸光度(UV-254),以及DOM中荧光物质含量的变化量高于上层水体.     

碳纳米管修饰电极电催化还原去除废水中的氯霉素

为发展废水中抗生素的处理技术、保护水环境质量,采用表面活性剂辅助分散碳纳米管,制备碳纳米管修饰电极,研究了修饰电极对氯霉素的电催化还原能力和动力学特征,初步探讨了氯霉素的还原去除机制.结果表明,双十六烷基磷酸(DHP)可以有效分散碳纳米管,通过优化碳纳米管和DHP的配比、分散液修饰量,制备的碳纳米管修饰电极还原2 mg·L~(-1)氯霉素24 h时的去除率达到97.21%;电催化还原氯霉素的动力学过程符合一级反应动力学模型,去除速率常数为0.157 4 h~(-1),半衰期为4.40 h.采用液相色谱-串联质谱分析法(LC-MS/MS)鉴定了氯霉素的还原产物,分析了氯霉素还原的可能途径,电催化不仅还原了氯霉素中的硝基,还可以进一步还原羰基和脱氯,显著降低氯霉素的毒性.     

Removal of heavy metals from aqueous solution by carbon nanotubes: adsorption equilibrium and kinetics

IntroductionWastewatersfrombatterymanufacturing ,printing ,painting ,dyeingandotherindustrialprocessesoftencontainconsiderableamountsofheavymetalsthatwouldendangerpublichealthifdischargedwithoutadequatetreatment.Long termingestionofwatercontaininghigherco…     

邻苯二甲酸酯及邻苯二甲酸在碳管上的吸附

以邻苯二甲酸（PA）和邻苯二甲酸二乙酯（DEP）为目标污染物,碳纳米管（CNTs）为吸附剂,通过不同pH值条件下单、双溶质的吸附实验,结合能量分布理论,分析PA对DEP在CNTs上的竞争和取代吸附.结果表明,在同一pH值下,DEP在CNTs上的吸附性强于PA.对于DEP,pH值改变导致的CNTs分散稳定性的变化是影响其吸附的决定因素.对于PA,溶液pH值会影响CNTs的表面电荷及PA的解离程度,两者均会产生影响.双溶质体系下,PA对DEP在CNTs上的吸附存在竞争和取代效应.在不同pH值条件下,PA对DEP在CNTs上的竞争和取代的程度与CNTs的分散稳定性和PA的解离程度有关.基于能量分布的分析表明,虽然PA的加入导致DEP在CNTs上可利用的高能吸附位点数量显著下降,但是其可利用的低能吸附位点数量增加.     

Application of multiwalled carbon nanotubes treated by potassium permanganate for determination of trace cadmium prior to flame atomic absorption spectrometry

In this study we investigated the enrichment ability of oxidized multiwalled carbon nanotubes (MWCNTs) and established a new method for the determination of trace cadmium in environment with flame atomic absorption spectrometry.The MWCNTs were oxidized by potassium permanganate under appropriate conditions before use as preconcentration packing.Parameters influencing the recoveries of target analytes were optimized.Under optimal conditions,the target analyte exhibited a good linearity (R~2=0.9992) over the concentration range 0.5-50 ng/ml.The detection limit and precision of the proposed method were 0.15 ng/ml and 2.06%, respectively.The proposed method was applied to the determination of cadmium in real-world environmental samples and the recoveries were in the range of 91.3%-108.0%.All these experimental results indicated that this new procedure could be applied to the determination of trace cadmium in environmental waters.