单壁纳米碳管的纯化研究

A purification method to remove the metal catalysts and impurity carbon materials from arc-discharge-grown single-walled carbon nanotubes (SWCNTs) has been developed. Microporous membrane and the oxidation in the air for the crude SWCNTs were used to eliminate the coexisting metal catalysts nanoparticles，carbon nanoparticles and amorphous carbon. Then we used the high resolution transmission electron microscopy (HRTEM) to characterize the crude SWCNTs prepared by arc-discharge method and the purified SWCNTs. The Raman spectra and the thermogravimetric analysis (TGA) were also utilized to analyze the approach of our purification for SWCNTs. With this method the SWCNTs with the purity more than 95% could be obtained.     

单壁纳米碳管的纯化及表征

利用微孔膜及空气氧化法逐步除去电弧放电法制备的单壁纳米碳管(SWCNTs)中的金属催化剂粒子、碳纳米粒子、无定形碳等杂质,并利用热重分析（TGA）、高分辨透射电子显微镜（HRTEM）及拉曼（Raman）光谱,对每一步得到的产物进行分析表征.实验证明,该方法对单壁纳米碳管的纯化是比较有效的,可以得到纯度在90％以上的单壁纳米碳管.     

非共价法分离光学活性单壁碳纳米管

单壁碳纳米管（SWNTs）由于具有独特的物理、化学性质,激起人们极大的研究兴趣。目前生产的SWNTs通常包含等量左旋和右旋对映异构体,无光学活性,极大地限制碳纳米管在光学和光电子领域的研究和应用。已报道的非共价法分离光学活性碳纳米管的方法主要有离子交换色谱法、nanotweezers选择法、密度梯度超高速离心法、共轭聚合物缠绕法和小分子吸附法。本文较为详尽地综述了非共价法分离光学活性碳纳米管的研究进展,对各种分离方法的机理进行阐述,并在此基础上分析这些方法和分离效果的关系,指导设计和合成新型的分离试剂。最后,本文还针对上述研究中存在的问题,提出了旋光性SWNTs分离技术的研究方向。     

担体负载单壁碳纳米管采样吸附剂的制备及其性能研究

将单壁碳纳米管负载于白色101担体上,制备了新型采样吸附剂S101.利用扫描电镜可观察到在101担体表面包覆的碳纳米管,粒度分布测试表明其粒径在180～250 μm之间; 通过BET(Brunauer emmett teller)吸附测得新型采样吸附剂的比表面积为16.8 m2/g,与Tenax TA大致相当; 热重实验表明, 其可耐400 ℃高温.采集不同湿度和储存不同的时间的样品, 测试回收率,采用冲洗色谱法分别测定常见挥发性有机化合物对S101的穿透体积,以及测试不同采样管的采样重现精度和分布体积对值,表明新型采样吸附剂具有湿度影响小、储存稳定的特点,对典型挥发性有机化合物都有较大的穿透体积,采样合格率达到100%.此吸附剂不仅保留了单壁碳纳米管原有优良的吸附性能,而且有效改善了单壁碳纳米管吸附管采样透气性,显著提高了采样精密度,可以广泛应用于实际气体样品采集.     

DNA/Single-Walled Carbon Nanotubes Based Fluorescence Detection of Hg2+

A new, highly selective, and sensitive technique has been developed for the detection of Hg²⁺ using singled-wall carbon nanotubes (SWNTs) and two kinds of oligonucleotides. The fluorescence of the thymine-rich single stranded DNA labeled with dye (the probe ssDNA) was effectively quenched by the SWNTs. In the presence of a target DNA (rich T-T mismatched with probe), the tightness of the DNA wrapping around the SWNTs was loosened. Since binding of Hg²⁺ turned the T-T mismatches to stable T-Hg²⁺-T base pairs, and the binding rate of DNA and the nanotube was lower than that of DNA hybridization, it induced the release of DNA molecules from the SWNTs, and this resulted in a remarkable increase of fluorescence compared to that of the DNA-SWNTs. The assay exhibited a dynamic response range for Hg²⁺ from 4.52 × 10^?8 M to 7.21 × 10^?7 M with a detection limit of 10 nM.     

Capacitive and Charge Transfer Effects of Single-Walled Carbon Nanotubes in TiO2 Electrodes

The transfer of nanoscale properties from single-walled carbon nanotubes (SWCNTs) to macroscopic systems is a topic of intense research. In particular, inorganic composites of SWCNTs and metal oxide semiconductors are being investigated for applications in electronics, energy devices, photocatalysis, and electroanalysis. In this work, a commercial SWCNT material is separated into fractions containing different conformations. The liquid fractions show clear variations in their optical absorbance spectra, indicating differences in the metallic/semiconducting character and the diameter of the SWCNTs. Also, changes in the surface chemistry and the electrical resistance are evidenced in SWCNT solid films. The starting SWCNT sample and the fractions as well are used to prepare hybrid electrodes with titanium dioxide (SWCNT/TiO₂). Raman spectroscopy reflects the optoelectronic properties of SWCNTs in the SWCNT/TiO₂ electrodes, while the electrochemical behavior is studied by cyclic voltammetry. A selective development of charge transfer characteristics and double-layer behavior is achieved through the suitable choice of SWCNT fractions.     

单壁碳纳米管拉伸变形的原子尺度模拟

The molecular dynamics method was adopted to investigate the tension deformation for SWCNTs with different chiralities and radius. The results show that nanotubes have an extremely large breaking strain. Carbon nanotubes are completely ductile before their structural defects appear. Through tracing the evolution of the spacial configuration of a micro structural cell of SWCNTs, it is found that the torsion deformation results in the change of structural symmetry. Thus the load is no longer well distributed. The structural defects will occur with further loading. The systematic energy change of SWCNTs is observed. It can be seen that there is a structural transformation around the initial vacancy defects when the axial tension strain reaches a certain value. The two adjacent hexagons change to one pentagon and one heptagon (also called the Stone Wales transformation). The 5 7 configuration makes strain energy release, and the systematic energy falls. This configuration is more preferable from the viewpoint of the energy. The results also show that fewer defects have weak influence on the mechanical properties of SWCNTs under the present initial vacancy defect condition.     

Nanocomposite: Antimony Sulfide in Channels of Single-Walled Carbon Nanotubes

A nanocomposite of antimony sulfide Sb₂S₃ embedded into the channels of single-walled carbon nanotubes (SWCNTs) has been prepared for the first time by the capillary wetting method and has been characterized by X-ray powder diffraction, transmission electron microscopy (TEM), transmission scanning electron microscopy (TSEM), and X-ray energy dispersive (EDX) spectroscopy. Antimony sulfide fills the channels of almost all SWCNTs. Channel filling is continuous along the entire length of the tube up to 1 μm. The diameters of filled SWCNTs fall in the range 0.6–3.5 nm. The periodicity of Sb₂S₃ crystal clusters observed on electron microscopic images is 2.0–2.2 nm along the nanotube axis and 2.5–3.5 nm in the transverse direction. A structural model of a Sb₂S₃ cluster is suggested.     

单壁碳纳米管的CVD合成及管径分布

甲烷在以活性氧化铝为载体的Fe、Co、Ni、Ru等催化剂上于850 ℃分解并生成直径为0.8～5 nm的单壁碳纳米管.预先将催化剂在1100 ℃焙烧,能够减少产物中无定形碳的生成.拉曼光谱结果表明,由该法制备的碳纳米管的管径分布主要受温度的影响,较低温度有利于较小直径的单壁碳纳米管的生成和较好的管径选择性.     

NEXAFS光谱分析聚合物修饰的单壁碳纳米管

利用C1s、O1s、N1s近边X射线吸收精细结构(Near Edge X-Ray Absorption Fine Structure,NEXAFS)光谱对聚合物修饰的碳纳米管进行了分析,研究了氧化及偶联聚合物对碳纳米管结构的影响。氧化碳纳米管及十八胺修饰的、聚合物/十八胺双修饰的碳纳米管的NEXAFS光谱均出现了碳/氧K边π*(C=O)和σ*(C-O)共振峰;而十八胺修饰的、聚合物/十八胺双修饰的碳纳米管则出现了氮K边π*(N-C=O)和σ*(N1s)共振峰。分析表明,NEXAFS光谱可有效表征聚合物修饰的碳纳米管。     

Functionalization and Dissolution of Single-Walled Carbon Nanotubes by Chemical-Physical and Electrochemical Treatments

Single-Walled Carbon Nanotubes (SWCNTs) possess a wealth of exceptional structural, mechanical and electronic properties. These have made them potentially useful for applications in nanotube-reinforced materials, nanoelectronic devices, field emitters, probe tips for SPM, as well as for sensors, biosensors, and actuators. However, manipulation and processing of SWCNTs has been limited by their insolubility in most common solvents, although some dissolution has recently been obtained. Their chemical modification might pave the way to many useful applications, including the preparation of composite materials or the immobilization of biological molecules as enzymes (i.e., for biosensors and electrochemical sensors). Attachment of oxygen-containing functional groups (i.e., carboxy groups, carbonyl groups, hydroxy groups, etc.) on the surface of the carbon nanotubes could be achieved using different pretreatments of the nanostructured material. These involved (a) chemical and physical procedures; and (b) electrochemical functionalization. Different attempts at sidewall modification have been hampered by the presence of significant contaminants as graphitic and amorphous carbon or have required solubilization via chemical reactions on the ends of cut nanotubes. A more accommodating and direct approach to functionalize nanotubes is therefore required. We report here the sidewall functionalization of purified SWCNTs, obtained by different approaches and finally, we can discuss possible applications of functionalized SWCNTs in the sensing area.     

共振增强拉曼光谱技术在单壁碳纳米管表征中的应用

共振增强拉曼光谱技术是表征和研究单壁碳纳米管(SWNTs)的有力工具, 它既能用于SWNTs的几何结构表征, 又能反映SWNTs的电子态密度信息. 特别指出的是, 由于共振拉曼效应, 它能够灵敏地检测单根SWNT的局域信息. 本文首先概述了SWNTs拉曼光谱的RBM峰、G峰、D峰和G'峰的特征和应用, 然后综述了共振增强拉曼光谱在SWNTs的结构表征、形变测量、缺陷测量和温度测量中的应用和进展, 最后讨论了共振拉曼光谱在SWNTs表征方面所面临的机会和挑战.     

Importance of Oxygen in the Metal-Free Catalytic Growth of Single-Walled Carbon Nanotubes from SiO(x) by a Vapor-Solid-Solid Mechanism

To understand in-depth the nature of the catalyst and the growth mechanism of single-walled carbon nanotubes (SWCNTs) on a newly developed silica catalyst, we performed this combined experimental and theoretical study. In situ transmission electron microscopy (TEM) observations revealed that the active catalyst for the SWCNT growth is solid and amorphous SiO(x) nanoparticles (NPs), suggesting a vapor-solid-solid growth mechanism. From in situ TEM and chemical vapor deposition growth experiments, we found that oxygen plays a crucial role in SWCNT growth in addition to the well-known catalyst size effect. Density functional theory calculations showed that oxygen atoms can enhance the capture of -CH(x) and consequently facilitate the growth of SWCNTs on oxygen-containing SiO(x) NPs.     

三步升温法合成阵列碳纳米管

本文使用结构简单的单温炉设备, 以二茂铁/三聚氰胺混合物为原料, 采用独特的三步升温方法于光滑的SiO₂衬底上合成出了大面积的阵列碳纳米管, 并对碳纳米管的形貌和结构进行了研究.     

超声分散对单壁碳纳米管分离的影响

利用凝胶柱色谱技术, 研究者们通过两步或多步淋洗的方法实现了不同导电属性或电子结构单壁碳纳米管(SWCNTs)的分离, 并提出其分离机制主要是由不同导电属性和电子结构的SWCNTs 与凝胶填料之间作用力的差异所导致的. 基于凝胶柱色谱分离技术, 本文重点考察了超声时间对单壁碳纳米管单分散以及金属型/半导体型SWCNTs 分离的影响. 在一定的低超声功率下, 适当增加超声时间有利于SWCNTs 在十二烷基硫酸钠(SDS)溶液中的单分散. 紫外-可见-近红外(UV-Vis-NIR)吸收光谱、拉曼(Raman)光谱和荧光(PL)光谱表征结果表明, 2 h的超声条件是获得高纯度的金属型以及不同直径分布的半导体型SWCNTs 的最优条件. 我们认为不同超声时间对SWCNTs 分离的影响主要是改变了SWCNTs 的单分散性和长度, 调制了不同SWCNTs 与凝胶之间作用力的差异, 从而导致了不同SWCNTs分离结果.     

NaCl对琼脂糖凝胶电泳法分离单壁碳纳米管的影响

如何获得单一导电属性的单壁碳纳米管(SWCNT),使其在各领域得到更广泛的应用,引起了科研人员越来越多的关注.琼脂糖凝胶电泳(AGE)法以其简便,低成本,可规模化等优点在分离金属型(m-)和半导体型(s-)单壁碳纳米管的诸多分离方法中体现出独特的优势.本文利用紫外-可见-近红外(UV-Vis-NIR)吸收光谱分析手段,系统研究了NaCl的添加对AGE法分离SWCNT的影响.研究发现NaCl的添加对SWCNT的分离有一定的影响:当NaCl添加量低于70 mmol.L-1时,可以提高分离后体系中s-SWCNT的相对含量;当NaCl添加量高于70mmol.L-1时,随着添加量的增加,NaCl的加入开始抑制m-SWCNT和s-SWCNT的有效分离;当NaCl添加量达到160 mmol.L-1时体系分离效率明显降低.我们推测这种影响主要是由盐的添加改变了分散剂在m-SWCNT和s-SWCNT表面的吸附结构引起的.     

溶胶-凝胶法可控制备氧化锡纳米晶包覆碳纳米管

采用溶胶-凝胶法制备了氧化锡纳米晶包覆的碳纳米管。自由Sn4+离子从稳定的Sn柠檬酸配合物中缓慢释放出来,迁移到碳纳米管上,并在碳纳米管上沉积形成了SnO2纳米晶,沉积过程完全为异相成核方式,在碳纳米管外并没有发现单独的SnO2纳米晶。这种溶胶-凝胶方法还可以用来制备无氯离子污染的、低团聚的纯SnO2纳米晶。     

Measuring the Stability of Supramolecular Complexes in the Proximity of Single-Walled Carbon Nanotubes

The decoration of SWNTs with supramolecular motifs is a common strategy for their subsequent noncovalent functionalization. However, due to the lack of a standard methodology, there are no quantitative measurements showing the extent to which the supramolecular equilibria are affected by one of the host-guest couple being anchored to the SWNT. Here, we use a method we initially developed to quantify association of small organic molecules to the walls of SWNTs to compare association constants of two host-guest systems, a Hamilton receptor-cyanuric acid derivative and a crown ether-ammonium couple, in solution and when the host is covalently attached to the SWNTs. Our data show that association does occur, but the stability of the complexes is significantly affected, as reflected in a sizable reduction in their association constant, when compared to solution.