多壁碳纳米管对三丁基锡的吸附行为及其细胞毒性效应研究

研究了多壁碳纳米管对三丁基锡(TBT)吸附行为,主要考察了溶液pH和盐度的影响作用.同时比较了无机锡、四丁基锡(TeBT)与三丁基锡在多壁碳纳米管上吸附行为的差异,并探讨了在多壁碳纳米管存在下三丁基锡的细胞毒性作用.研究结果表明多壁碳纳米管对丁基锡具有较强的吸附能力,吸附平衡时问短,能很快达到吸附平衡.溶液pH能影响这种吸附作用.三丁基锡在多壁碳纳米管上的吸附符合Langmuir和Freundlich吸附等温式,主要为疏水作用.在与多壁碳纳米管的共存体系中三丁基锡的细胞毒性效应有所削弱,这可能与多壁碳纳米管对三丁基锡的吸附作用有关.     

邻苯二甲酸和苯甲酸在功能化碳纳米管上的吸附行为

在pH7.0的条件下,采用批量平衡方法研究邻苯二甲酸（PA）和苯甲酸（BA）在3种不同功能化碳纳米管（羟基化H-CNTs、羧基化C-CNTs和石墨化G-CNTs）上的吸附/解吸行为,并进一步探究共存BA对PA在碳纳米管上吸附的影响.结果表明,Langmuir和Freundlich模型均可对PA和BA在3种碳纳米管上的吸附数据进行较好的非线性拟合,其中Freundlich模型拟合效果更好（Adj r²均达到0.88以上）;3种碳纳米管对PA和BA的吸附能力大小均依次为：C-CNTs > H-CNTs > G-CNTs;解吸实验中,C-CNT和H-CNTs对BA和PA的解吸均具有明显的滞后现象,说明BA和PA在C-CNT和H-CNTs上的吸附有较强化学作用力的发生,而G-CNTs对二者的解吸曲线与吸附曲线几乎重合,不具有明显的滞后现象,这与G-CNTs表面缺乏官能团有关;当PA和BA共存在时,以PA为主要吸附质,BA为竞争吸附质,发现在H-CNTs和C-CNTs上,共存BA对PA为竞争作用,而在G-CNTs上,共存BA对PA起协同吸附作用.     

沉积物提取液对萘在河流沉积物中吸附-解吸行为的影响

疏水性有机污染物在沉积物上的吸附-解吸行为直接决定其在水环境中迁移、转化、生物效应与归宿.以往采用背景电解质溶液作为解吸体系的方法,忽略了其与天然水体水化学条件的差异可能对污染物的解吸行为产生的影响,从而造成疏水性有机污染物在天然水体沉积物上的吸附-解吸性能评价方法存在较大偏差.本文通过选用沉积物浸出液代替背景电解质溶液的方式来保证吸附-解吸水化学条件的一致性,采用批量平衡的方法对分别采集于凉水河水系(标记为L)以及东江流域(标记为D)的两种河流沉积物样品,进行连续吸附-解吸实验,以考察多环芳烃萘在沉积物上的吸附-解吸规律,从而阐明水化学条件的一致性对吸附-解吸过程的影响与重要性.实验结果表明,萘在沉积物上的吸附-解吸过程呈现出明显的滞后现象.传统的以背景电解质溶液作为介质,研究疏水性有机污染物解吸行为的方法会导致解吸体系的TOC值比模拟天然水体体系减少74.68%～85.01%,这种吸附-解吸水化学条件的差异会增强污染物在沉积物上的滞后性,具体表现为萘在沉积物L和D浸出液中的平均解吸量相比其在背景电解质溶液中分别增加了3.14mg·kg-1和2.40mg·kg-1,平均解吸滞后系数由在背景电解质溶液中的0.04和0.135降低至沉积物浸出液中的0.012和0.072.此现象表明,与纯电解质溶液比较,采用从沉积物中提取的溶解有机碳作为解吸介质,会显著增加萘在沉积物中的平均解吸量,所获得的实验结果更加符合天然水体的实际条件.     

菲在四种碳纳米管上的解吸行为研究

碳纳米材料是当前环境领域关注的热点之一.本研究以菲为模型污染物,以Tenax TA树脂为助解吸剂,研究了菲在4种碳纳米管上的非生物解吸动力学以及碳纳米管理化性质对菲解吸的影响机理.结果表明,当老化60d,碳纳米管上菲初始吸附量为578mg·kg-1时,解吸30d后菲累积解吸量随时间变化不明显,解吸35d后碳纳米管上菲的...     

两种染料与阿特拉津在沉积物上的竞争吸附

通过批量吸附实验研究了两种染料对阿特拉津(AT)在天然水体沉积物上吸附的影响.结果表明,与对照相比,刚果红(CR)和亚甲基蓝(MB)在实验浓度范围内均与AT发生竞争吸附,分别使AT的吸附率降低了14.29%和30.16%.共存体系的溶液化学条件发生变化时,AT的吸附有所不同.当体系pH值和温度升高时,AT的吸附量减小;而离子强度的升高,促使AT在沉积物上的吸附量增大.     

对印染废水中甲基橙去除的新方法研究

本文主要研究了碳纳米管-铁氧化物磁性复合材料(磁性碳纳米管)在吸附处理甲基橙方面的应用。分别研究了甲基橙初始浓度、吸附剂投加量、吸附时间、溶液温度和p H值等工艺条件对甲基橙吸附率的影响。结果表明,在甲基橙初始浓度为2 mg/L,吸附剂投加量4 g/L,吸附时间30min,p H值为3的条件下,吸附率达到了63.99%。磁性碳纳米管吸附甲基橙的吸附率随着吸附剂的用量增大而增大;在20 min以前,甲基橙的吸附率随着时间的增加而增大,到达30 min后吸附率基本保持不变;甲基橙的吸附率随着起始甲基橙的浓度的增加而减小。另外,酸性溶液有利于磁性碳纳米管吸附甲基橙,随着p H的增大吸附率逐渐减小,当溶液呈碱性时,p H对吸附率的影响逐渐减小。     

碳纳米管对孔雀石绿的吸附特性

该文研究了碳纳米管对水中孔雀石绿的吸附性能。结果表明,碳纳米管对孔雀石绿的吸附平衡时间约为4 h左右;假二级动力学模型更适合描述碳纳米管对孔雀石绿的吸附;碳纳米管对水中孔雀石绿的吸附主要受外部传质影响;Langmuir等温模型拟合吸附数据效果最佳,并且最大吸附量为104.49 mg/g(288 K);由D-R等温模型可计算出吸附平均能量分别为29.79(288 K)、30.03(298 K)、28.05(308 K)k J/mol;吸附机制主要以化学吸附为主;随着温度的升高,碳纳米管对孔雀石绿的吸附逐渐降低;碳纳米管对孔雀石绿的吸附行为是自发进行的放热反应;离子强度的增大对吸附量有促进作用;在酸性条件下,碳纳米管对孔雀石绿的吸附量随p H的增加而增大。     

巯基硅烷改性多壁碳纳米管的合成及其对Cd2+的吸附性能研究

利用3-巯丙基三甲氧基硅烷(MPTMS)作硅烷偶联剂对多壁碳纳米管(MWCNTs)进行改性,制备巯基硅烷改性多壁碳纳米管(SHMWCNTs),并进行了SH-MWCNTs对Cd~(2+)的批量吸附实验.同时,利用扫描电镜(SEM)、X射线光子能量仪(EDS)、红外光谱(FT-IR)对SHMWCNTs进行表征,探究了溶液初始pH、吸附剂投加量、吸附时间、溶液初始Cd~(2+)浓度等因素对吸附效果的影响,分析了吸附动力学特征及吸附等温线特征,初步探讨了吸附机理.SEM、EDS与FT-IR图谱显示,MPTMS已成功接枝到MWCNTs表面,表明SH-MWCNTs制备成功.吸附时间为90 min,pH为4时的吸附效果最佳,吸附量随SH-MWCNTs投加量、Cd~(2+)浓度的增加而增大.吸附动力学和吸附等温线研究表明,SHMWCNTs对Cd~(2+)的吸附动力学符合准二级线性方程,吸附等温线符合Freundlich、Langmuir 2种模型,吸附以单分子层吸附为主,也存在层间扩散的多层吸附.     

氧氟沙星在碳纳米管上的吸附机制研究

碳纳米管吸附氧氟沙星(OFL)是控制其在水体中归趋的一种有效方法.本研究讨论了多壁碳纳米管及其共混酸处理产物(MWCNTs和MWCNTs-O)对于氧氟沙星的吸附过程.考察了吸附动力学、吸附等温线、pH的影响和解吸过程.结果表明,吸附动力学曲线符合准二级动力学模型,OFL在MWCNTs-O上的平衡吸附量较大;Langmuir模型和Freundlich模型都能很好拟合吸附过程;pH在6.0~10.0时,平衡吸附量下降很快;解吸过程出现了解吸滞后现象,在MWCNTs-O上更为明显.吸附热力学分析表明OFL在碳纳米管上的吸附作用力为分子间作用力,MWCNTs-O上较多含氧官能团的引入为OFL分子的吸附提供了较多的吸附点,有利于OFL分子和碳纳米管之间形成相对作用力较强的氢键,该作用力主导了OFL在碳纳米管上的吸附,解释了试验现象.     

硝酸处理的碳纳米管吸附水溶液中汞离子的研究

碳纳米管是一种具有独特结构和优异性能的纳米材料。该文研究了硝酸处理的碳纳米管作为吸附剂吸附水溶液中的汞离子的吸附特性,考察了溶液pH值、吸附时间、溶液浓度以及吸附剂的量等因素对吸附行为的影响。实验结果表明:在pH值为2～5的范围内,碳纳米管对汞离子的吸附量随着pH值的增大而增大,并在pH为5时(对汞离子的吸附量)达到了最大值,在pH大于5时,pH值对吸附效果影响不大。碳纳米管吸附汞离子的量随着吸附时间的增加而增大,且在60min内达到了吸附平衡,当Hg2+浓度为20mg/L时吸附量为16.63mg/g。通过对Langmuir和Freundlich方程对吸附等温线的拟合比较,Langmuir方程更适合描述吸附特性。随着吸附剂量增加,吸附效率上升。研究结果表明,硝酸处理的碳纳米管是一种有效的水溶液中汞离子的吸附剂。     

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.     

Adsorptive removal of hydrophobic organic compounds by carbonaceous adsorbents: A comparative study of waste-polymer-based, coal-based activated carbon, and carbon nanotubes

Adsorption of the hydrophobic organic compounds (HOCs) trichloroethylene (TCE), 1,3-dichlorobenzene (DCB), 1,3-dinitrobenzene (DNB) and γ-hexachlorocyclohexane (HCH) on five different carbonaceous materials was compared. The adsorbents included three polymer-based activated carbons, one coal-based activated carbon (F400) and multiwalled carbon nanotubes (MWNT). The polymerbased activated carbons were prepared using KOH activation from waste polymers: polyvinyl chloride (PVC), polyethyleneterephthalate (PET) and tire rubber (TR). Compared with F400 and MWNT, activated carbons derived from PVC and PET exhibited fast adsorption kinetics and high adsorption capacity toward the HOCs, attributed to their extremely large hydrophobic surface area (2700 m²/g) and highly mesoporous structures. Adsorption of small-sized TCE was stronger on the tire-rubber-based carbon and F400 resulting from the pore-filling effect. In contrast, due to the molecular sieving effect, their adsorption on HCH was lower. MWNT exhibited the lowest adsorption capacity toward HOCs because of its low surface area and characteristic of aggregating in aqueous solution.     

Noncovalent immobilization of manganese peroxidases from P. chrysosporium on carbon nanotubes

Manganese peroxidases (MnP) from Phanerochaete chrysosporium were adsorbed onto multi-walled carbon nanotubes (MWNT). Four different loadings of MnP on MWNTs were investigated, and the maximum enzyme loading of 47.5 μg/mg of MWNTs was obtained in 12 h. The adsorbed MnP showed a catalytic activity of up to 0.1 U/mg of the weight of the system of MnP/MWNTs, with 23% of its original activity retained. The AFM image of the adsorbed enzymes indicated that a layer of MnP covered the surface of the MWNTs and retained its original three-dimensional shape. Amino-based nonspecific interactions may play the dominant role in the adsorption of MnP on MWNTs.     

碳纳米管对水中4-氯酚和2,4-二氯酚的吸附性能研究

碳纳米管是一种具有独特结构和优异性能的新型纳米材料。文章利用碳纳米管对水溶液中的4-氯酚和2,4-二氯酚进行了吸附研究,考察了吸附时间、pH值、温度等对吸附效果的影响,并采用Langmuir和Freundlich方程进行拟合,探讨了其可能的吸附机理。研究结果表明,碳纳米管对4-氯酚和2,4-二氯酚的最佳吸附酸度在pH=2～6。碳纳米管对2,4-二氯酚吸附量大于对4-氯酚的吸附量,二者动力学特征均符合准二级动力学方程。研究了4-氯酚和2,4-二氯酚在碳纳米管上的吸附等温线。研究结果表明:4-氯酚和2,4-二氯酚在碳纳米管上的吸附量随着温度的升高而下降。吸附过程是一个放热的过程,Langmuir和Freundlich等温吸附方程均能较好地拟合吸附等温线。碳纳米管能较好地用于除去水溶液中的4-氯酚和2,4-二氯酚。     

碳纳米管径向尺寸对碳纳米管自支撑膜孔隙结构及通量的影响

为了探索碳纳米材料膜在水处理中应用的可能性,本实验选取4种径向尺寸的碳纳米管(Carbon Nanotubes, CNTs),采用压力辅助过滤技术制备CNTs自支撑膜.通过对CNTs自支撑膜的平均孔径、孔径分布及截留分子量(Molecular weight Cut-Off,MWCO)等进行分析,研究了CNTs径向尺寸变化对CNTs自支撑膜孔隙结构的影响.结果表明,CNTs的径向尺寸越小,制备得到的CNTs自支撑膜越趋向于形成小孔径的膜孔,且孔径分布更加均匀,孔隙面积比越高,膜的MWCO越小.单壁碳纳米管(Single-walled carbon nanotube, SWNT)与多壁碳纳米管(Multi-walled carbon nanotube, MWNT)相比,前者更容易形成膜平均孔径更小且孔径分布更均匀的CNTs自支撑膜.膜通量测定结果表明,研究制备的CNTs自支撑膜的通量属于低压膜范围,通量在230～347 L·m~(-2)·h~(-1)·bar~(-1)之间.其中,虽然由径向尺寸较小的CNTs所制备的CNTs自支撑膜的平均孔径更小,但由于其具有更高的孔隙面积比和更小的膜厚度,其纯水通量相对高于由大径向尺寸CNTs制备的CNTs自支撑膜.     

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.     

功能化材料Zr@AC对水中难降解农药阿特拉津的去除特征

我国农药阿特拉津的污染十分严重,对生态系统造成了非常不利的影响. 为了实现对水环境中阿特拉津的高效去除和吸附剂的重复利用,该研究通过溶液浸渍和高温煅烧技术将金属锆负载到活性炭上,制备出功能化材料Zr@AC,使用扫描电镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外吸收光谱仪(FTIR)和比表面及孔径分析仪(BET)对材料的形貌和组成进行了表征,并考察了Zr@AC对水中阿特拉津的去除效果. 结果表明:①当浸渍液锆离子的质量分数为7.0%、浸渍时间为9.0 h、煅烧温度为500 ℃和煅烧时间为5.0 h时,制备的Zr@AC具有较大的比表面积、较多的中孔和微孔以及丰富的活性位点. ②对阿特拉津的去除研究表明,当溶液pH为4.0、温度为25 ℃、Zr@AC投加量为60.0 mg/L时,经过90 min的反应,Zr@AC对阿特拉津的吸附容量最大,达到93.8 mg/g. ③动力学模拟研究表明,该吸附过程遵循拟二级动力学模型,且Freundlich等温吸附模型的拟合结果要优于Langmuir等温吸附模型,说明Zr@AC对阿特拉津的吸附存在化学吸附和多分子层吸附的双重作用. ④经过5次重复试验后,Zr@AC对阿特拉津的去除率仍有83.9%. 研究显示,Zr@AC可作为水中去除阿特拉津的吸附剂,是一种很有前途、可重复多次使用的材料.      

Preparation and characterization of a lipoid adsorption material and its atrazine removal performance

A novel adsorbent named lipoid adsorption material (LAM), with a hydrophobic nucleolus (triolein) and a hydrophilic membrane structure (polyamide), was synthesized to remove hydrophobic organic chemicals (HOCs) from solution. Triolein, a type of lipoid, was entrapped by the polyamide membrane through an interfacial polymerization reaction. The method of preparation and the structure of the LAM were investigated and subsequent experiments were conducted to determine the characteristics of atrazine (a type of HOC) removal from wastewater using LAM as the adsorbent. The results showed that LAM had a regular structure compared with the prepolymer, where compact particles were linked with each other and openings were present in the structure of the LAM in which the fat drops formed from triolein were entrapped. In contrast to the atrazine adsorption behavior of powdered activated carbon (PAC), LAM showed a persistent adsorption capacity for atrazine when initial concentrations of 0.57, 1.12, 8.31 and 19.01 mg/L were present, and the equilibrium time was 12 hr. Using an 8 mg/L initial concentration of atrazine as an indicator of HOCs in aqueous solution, experiments on the adsorption capacity of the LAM showed 69.3% removal within 6–12 hr contact time, which was close to the 75.5% removal of atrazine by PAC. Results indicated that LAM has two atrazine removal mechanisms, namely the bioaccumulation of atrazine by the nucleous material and physical adsorption to the LAM membrane. Bioaccumulation was the main removal mechanism.     

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.