Testing the resistance of fullerenes to chemothermal oxidation used to isolate soots from environmental samples

We tested the resistance of five different fullerenes (C₆₀, C₇₀, C_76/78 mix, and C₈₄) to chemothermal oxidation at 375 °C (CTO-375), a method that has been used and tested for quantifying black carbon (BC) and CNTs in soils and sediments. C₆₀ survived CTO-375 the most (50%), while C₇₀ was the fullerene with the lowest survival rate (<1%). Standard additions of C₆₀ to soil and sediment reference materials yielded recoveries between 18 and 36%. Although lower than recoveries previously observed for soot and CNTs, these results demonstrate the capability of CTO-375 to partially isolate C₆₀ from solid environmental matrices. Standard additions of C₇₀, C_76/78, and C₈₄ yielded slightly higher survival rates when added to soil and sediment than in their pure form. These results indicate that the mineral matrices of these samples probably had a catalytic effect towards C₆₀ and a protective effect towards C₇₀, C_76/78, and C₈₄ during CTO-375.     

A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO₂:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O₂⁻ radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

沉积物中不同浓度多壁碳纳米管对Cd和BDE-47生态毒性的影响

随着碳纳米管的广泛应用,其将不可避免地进入环境中.由于其具有极好的吸附亲和力和吸附容量,碳纳米管可以充当环境中持久性有毒污染物的载体,从而改变共存污染物的生物有效性和生态毒性.为评价淡水沉积物中不同多壁碳纳米管(MWCNTs)对Cd和BDE-47生态毒性的影响,采用沉积物慢性生物测试研究了不同浓度MWCNTs存在下Cd和BDE-47对铜锈环棱螺肝胰脏抗氧化防御系统关键成分超氧化物歧化酶(SOD)与Ⅱ相解毒反应的关键酶谷胱甘肽-S-转移酶(GST)以及脂质过氧化损伤指标丙二醛(MDA)的影响.结果表明,沉积物中低浓度MWCNTs(0.5 mg·g~(-1))增强Cd对铜锈环棱螺的氧化胁迫,中、高浓度(5、50 mg·g~(-1))MWCNTs引起Cd对铜锈环棱螺的氧化损伤,MWCNTs的存在显著增强了沉积物中Cd对铜锈环棱螺的毒性,而且具有浓度-效应关系;低浓度MWCNTs不影响BDE-47对铜锈环棱螺的毒性,中、高浓度MWCNTs显著降低BDE-47的毒性,同样具有明显的浓度-效应关系.因此,在评价MWCNTs的潜在环境风险时,不仅考虑MWCNTs自身的毒性,还应当考虑MWCNTs的浓度、共存污染物的种类和MWCNTs与共存污染物之间的相互作用.     

Evaluation of micro- and nano-carbon-based adsorbents for the removal of phenol from aqueous solutions

This work reports on the adsorption efficiency of two classes of adsorbents: nano-adsorbents including carbon nanotubes (CNTs) and carbon nanofibers (CNFs); and micro-adsorbents including activated carbon (AC) and fly ash (FA). The materials were characterized by thermogravimetric analysis, transmission electron microscopy, Brunauer–Emmett–Teller (BET) specific surface area, zeta potential, field emission scanning electron microscopy, and UV spectroscopy. The adsorption experimental conditions such as pH of the solution, agitation speed, contact time, initial concentration of phenol, and adsorbent dosage were optimized for their influence on the phenol. The removal efficiency of the studied adsorbents has the following order: AC > CNTs > FA > CNFs. The capacity obtained from Langmuir isotherm was found to be 1.348, 1.098, 1.007, and 0.842 mg/g of AC, CNTs, FA, and CNFs, respectively, at 2 hours of contact time, pH 7, an adsorbent dosage of 50 mg, and a speed of 150 rpm. The higher adsorption of phenol on AC can be attributed to its high surface area and its dispersion in water. The optimum values of these variables for maximum removal of phenol were also determined. The experimental data were fitted well to Langmuir than Freundlich isotherm models.     

TiO_2纳米管修饰电极处理反渗透浓水研究

研制了新型的TiO2纳米管修饰电极,应用于反渗透膜浓水的电化学氧化处理;利用扫描电镜和线性极化曲线对电极进行了表征;考察了电解时间、电流密度和pH值因素对电化学氧化处理反渗透膜浓水的影响;并分析了电极对反渗透浓水中各有机物组分的去除效果。实验结果表明TiO2纳米管修饰电极对反渗透浓水具有较高的电催化性能。     

单壁碳纳米管致昆明小鼠脑组织的氧化损伤

单壁碳纳米管(single walled carbon nanotubes,SWCNTs)是纳米材料研究关注的焦点之一.尽管如此,关于其神经毒性的研究相对较少.本研究将SWCNTs以不同的浓度(0 mg·kg-1·d-1,3.125 mg·kg-1·d-1,6.25 mg·kg-1·d-1,12.5 mg·kg-1·d-1),通过腹腔注射于Kunming小鼠体内.神经行为学实验(旷场实验)结果表明,在一定浓度的SWCNTs作用下,小鼠的情绪受到一定的影响,具有抑郁症的特征,出现移动能力下降,紧张等现象.同时小鼠脑部组织的活性氧族(reactive oxygen species,ROS)和丙二醛(malondialdehyde,MDA)水平升高(p0.05),还原型谷胱甘肽(glutathione,GSH)水平降低(p0.05),炎症因子白介素-1β(interleukin-1 beta,IL-1β)的水平升高(p0.05).组织学观察显示,随着染毒浓度的升高,脑海马锥体细胞的空泡化程度愈加明显,着色不均,锥体细胞顶状树突逐渐消失,细胞排列松散,尼氏小体消失.结论:一定浓度的SWCNTs可以导致小鼠脑组织发生病变,产生一定的神经毒性.     

生物电催化方法处理三氯乙酸的研究

利用吸附法将血红蛋白(Hb)固定在碳纳米管修饰电极表面,研究了Hb在碳纳米管修饰电极的直接电化学行为.固载Hb碳纳米管修饰电极在pH=7.0的PBS缓冲溶液中于-0.300V(vsSCE)处有一对相当可逆的循环伏安还原氧化峰,为Hb血红素辅基Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰.利用循环伏安法和恒电位电解法研究了固载Hb的碳纳米管修饰电极对有机氯模型污染物三氯乙酸的电催化还原脱氯,并通过鉴定中间产物探讨了其催化还原机理.结果表明,固载Hb的碳纳米管修饰电极对三氯乙酸的还原具有很高的催化活性,三氯乙酸是按照三氯乙酸→二氯乙酸→一氯乙酸→乙酸的途径分布还原脱氯.将固载Hb的碳纳米管修饰电极组装成三维填充床电解反应器,进行了三氯乙酸连续流动电解还原的初步研究.-0.6V(vs.SCE)电解180min,三氯乙酸去除率为40.13%.     

CNTs-CeO_2/H_2O_2复合光催化氧化体系降解水中酸性橙Ⅱ

运用"化学沉淀法",将Ce O2负载到碳纳米管(CNTs)上制备复合光催化剂,采用"单因素实验法"优化了制备条件。运用透射电镜和X射线衍射仪对复合光催化剂进行了表征。结果表明,负载到CNTs上的Ce O2为多晶面心立方结构,尺寸大小在6~10 nm之间,其在CNTs上分散效果好,负载均匀且负载率高。在溶液p H为5,CNTs-Ce O2用量为0.50g/L并光照2 h后,酸性橙Ⅱ的光脱色率和TOC去除率分别达到64.71%和44.25%;加入0.02 mmol/L H2O2后,CNTsCe O2/H2O2复合体系对酸性橙Ⅱ的光脱色率和TOC去除率分别提高至91.35%和82.40%。这预示着CNTs-Ce O2/H2O2复合光催化氧化体系在对水中偶氮染料的光催化处理方面具有潜在的应用价值。     

钯修饰碳纳米管电极电催化氧化三氯生

采用钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生,考察了极板间距、电流密度、离子强度、pH、初始浓度和电解时间对三氯生去除效率的影响,并探讨了其反应动力学。结果表明:钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生的最佳条件为:三氯生初始浓度为50 mg/L,电流密度约为10 mA/cm2,极板间距为1 cm,pH为11,电解质Na2SO4浓度为1 000 mg/L。此条件下,反应时间为3 h时三氯生的去除率可达到99%以上,三氯生的降解为零级反应。