湿法纯化碳纳米管阵列及其对碳纳米管阵列形貌的影响

采用酸溶液处理方法对垂直于衬底生长的碳纳米管阵列的纯化进行了研究. 利用扫描电子显微镜、X射线光电子能谱等手段对纯化前后的碳纳米管阵列的结构、形貌及化学组成进行表征. 实验结果表明, 通过控制条件, 酸溶液处理方法能够在有效地去除催化剂粒子等杂质的同时又保持阵列的相对完整性. 纯化后的碳纳米管阵列会促进其在电子学领域的进一步应用.     

Growth Mechanism of Vertically Aligned Carbon Nanotube Arrays

Vertically aligned multi-walled carbon nanotube arrays grown on quartz substrate are obtained by co-pyrolysis of xylene and ferrocene at 850 oC in a tube furnace. Raman spectroscopy and high resolution transmission electron microscopy measurements show that the single-walled carbon nanotubes are only present on top of vertically aligned multi-walled carbon nanotube arrays. It has been revealed that isolated single-walled carbon nanotubes are only present in those floating catalyst generated materials. It thus suggests that the single-walled carbon nanotubes here are also generated by floating catalyst. Vertically alignedcarbon nanotube arrays on the quartz substrate have shown good orientation and good graphitization. Meanwhile, to investigate the growth mechanism, two bi-layers carbon nan-otube films with di erent thickness have been synthesized and analyzed by Raman spectroscopy. The results show that the two-layer vertically aligned carbon nanotube films grow “bottom-up”. There are distinguished Raman scattering signals for the second layer itself, surface of the first layer, interface between the first and second layer, side wall and bottom surface. It indicates that the obtained carbon nanotubes follow the base-growth mechanism, and the single-walled carbon nanotubes grow from their base at the growth beginning when iron catalyst particles have small size. Those carbon nanotubes with few walls (typically <5 walls) have similar properties, which also agree with the base-growth mechanism.     

Achieving Direct Electrical Connection to Glucose Oxidase Using Aligned Single Walled Carbon Nanotube Arrays

Direct electron transfer between an electrode and the redox active centre of glucose oxidase, flavin adenine dinucleotide (FAD), is probed using carbon nanotube modified gold electrodes. Gold electrodes are first modified with a self‐assembled monolayer of cysteamine and then shortened single walled carbon nanotubes (SWNT) are aligned normal to the electrode surface by self‐assembly. The electrochemistry of these aligned nanotube electrode arrays is initially investigated using potassium ferricyanide which showed SWNT act as nanoelectrodes with the ends of the tubes more electrochemically active than the walls. Subsequently the nanotubes are plugged into the enzymes in one of two ways. In the first method, native glucose oxidase is covalently attached to the ends of the aligned tubes which allowed close approach to FAD and direct electron transfer to be observed with a rate constant of 0.3 s^?1. In the second strategy, FAD was attached to the ends of the tubes and the enzyme reconstituted around the surface immobilized FAD. This latter approach allowed more efficient electron transfer to the FAD with a rate constant of 9 s^?1.     

Aligned Carbon Nanotube Stationary Phases for Electrochromatographic Chip Separations

This paper reports a novel approach for developing a microfluidic electrochromatographic chip device using patterned vertically aligned carbon nanotubes as the stationary phase material. Patterned growth of nanotubes in a specific location of the channel is carried out using a solid phase Fe–Al catalyst as well as a vapor deposited ferrocene catalyst. Proof-of-concept applications are demonstrated using reversed phase capillary electrochromatographic separations as well as solid phase extraction of a glycosylated protein using concanavalin A immobilized onto the nanotube bed.     

Gold Nanoparticles Modified Titania Nanotube Arrays for Amperometric Determination of Ascorbic Acid

Development and use of highly ordered, vertically aligned TiO₂ nanotube arrays modified with gold nanoparticles for the selective detection of ascorbic acid (AA) in the presence of uric acid and glucose are reported here. Gold nanoparticles were electrodeposited on the Nanotube arrays by CV. The sensor was characterized using SEM, EDS, CV, and EIS. It showed very good performance with a sensitivity of 46.8 μA mM^?1 cm^?2, response time below 2 seconds and linearity in the range of 1 μM to 5 mM with a detection limit of 0.1 μM and was tested for the AA concentration in pharmaceutical preparations.     

Electrochemical Characterization of Vertically Aligned Carbon Nanofiber Arrays Prepared by Hole‐mask Colloidal Lithography

Nanoelectrode arrays consisting of vertically aligned carbon nanofibers were prepared through plasma enhanced chemical vapor deposition and patterned using hole‐mask colloidal lithography (HCL), a simple fabrication method employed as a cost‐effective patterning alternative to the conventional electron beam lithography. The density of the carbon nanofibers was easily altered by changing the concentration of the polystyrene spheres employed in HCL. Cyclic voltammetry and chronoamperometry were used to electrochemically characterize the arrays of different density. Results indicate that the density of the carbon nanofibers leads to differences in the macro/micro electroactive surface areas.     

Inlaid Multi‐Walled Carbon Nanotube Nanoelectrode Arrays for Electroanalysis

The rapid development in nanomaterials and nanotechnologies has provided many new opportunities for electroanalysis. We review our recent results on the fabrication and electroanalytical applications of nanoelectrode arrays based on vertically aligned multi‐walled carbon nanotubes (MWCNTs). A bottom‐up approach is demonstrated, which is compatible with Si microfabrication processes. MWCNTs are encapsulated in SiO₂ matrix leaving only the very end exposed to form inlaid nanoelectrode arrays. The electrical and electrochemical properties have been characterized, showing well‐defined quasireversible nanoelectrode behavior. Ultrasensitive detection of small redox molecules in bulk solutions as well as immobilized at the MWCNT ends is demonstrated. A label‐free affinity‐based DNA sensor has shown extremely high sensitivity approaching that of fluorescence techniques. This platform can be integrated with microelectronics and microfluidics for fully automated microchips.     

Nanotube Content in Arc Generated Carbon Powder

 A novel experimental technique for the separation of nanotubes from other unwanted carbon species in arc generated carbon soot is described. A conjugated polymer was used to bind to nanotubes in solution. The resultant hybrid was soluble, whereas extraneous carbon material formed a sediment at the bottom of the sample bottle. The process was monitored using electron paramagnetic resonance (EPR) spectroscopy showing that 63% of nanotubes were kept in solution and 98.1% of impurities were rejected. This non-destructive purification allowed the calculation of the nanotube content in the carbon soot using EPR and thermogravimetric analysis (TGA). The measurement of nanotube content gave a purity value of 34% for the soot used in this study; this is compatible with estimates from electron microscopic determinations.     

3-D carbon nanotube structures used as high performance catalyst for oxygen reduction reaction

We report a high performance oxygen reduction reaction (ORR) catalyst based on vertically aligned, nitrogen-doped carbon nanotube (VA-NCNT) arrays. Characterization in conditions analogous to the operation of a polymer electrolyte membrane fuel cell show ORR taking place on the catalyst at a favorable reduction potential with a superior current density and greater rate constant.     

阳极氧化法制备TiO_2纳米管阵列膜及其应用

由阳极氧化法制备的TiO2纳米管阵列,因其独特的有序结构而显示出优异的性能,在许多领域有着广泛的应用,成为一种很有发展前景的新型纳米结构材料。本文简要综述了制备TiO2纳米管阵列结构的方法及其应用研究进展。在比较了当前几种制备TiO2纳米管阵列方法的优缺点后,重点讨论了阳极氧化法制备TiO2纳米管阵列结构过程中,如何通过调整工艺参数来实现此类纳米管阵列结构的可控生长。最后评述了TiO2纳米管阵列材料研究的发展趋势和应用前景。     

Nanotube Content in Arc Generated Carbon Powder

Summary.  A novel experimental technique for the separation of nanotubes from other unwanted carbon species in arc generated carbon soot is described. A conjugated polymer was used to bind to nanotubes in solution. The resultant hybrid was soluble, whereas extraneous carbon material formed a sediment at the bottom of the sample bottle. The process was monitored using electron paramagnetic resonance (EPR) spectroscopy showing that 63% of nanotubes were kept in solution and 98.1% of impurities were rejected. This non-destructive purification allowed the calculation of the nanotube content in the carbon soot using EPR and thermogravimetric analysis (TGA). The measurement of nanotube content gave a purity value of 34% for the soot used in this study; this is compatible with estimates from electron microscopic determinations. Received June 23, 2000. Accepted July 3, 2000     

Electrochemical modification of vertically aligned carbon nanotube arrays

Electrochemical oxidation and reduction were utilized to modify vertically aligned carbon nanotube (CNT) arrays grown on a porous network of conductive carbon microfibers. Ultrafast and complete CNT opening and purification were achieved through electrochemical oxidation. Highly dispersed platinum nanoparticles were then uniformly and densely deposited as electrocatalysts onto the surface of these CNTs through electrochemical reduction. Using supercritical drying techniques, we demonstrate that the unidirectionally aligned and laterally spaced geometry of the CNT arrays can be fully retained after being subjected to each step of electrochemical modification. The open-tipped CNTs can also be electrochemically detached in full lengths from the supporting substrates and harvested if needed.     

自组装半导体碳纳米管薄膜的光电特性

采用自组装的方法制备99%高纯度半导体碳纳米管平行阵列条带,以金属钯和钪为非对称接触电极制备碳纳米管(CNT)薄膜晶体管(TFTs)器件.主要研究不同沟道长度碳纳米管薄膜晶体管器件的电输运特性和红外光电响应特性,分析了其中的载流子输运和光生载流子分离的物理机制.我们发现薄膜晶体管器件的电学性能和光电性能依赖于器件沟道长度(L)和碳纳米管的平均长度(LCNT).当沟道长度小于碳纳米管的平均长度时,器件开关比最低;当沟道长度超过碳纳米管平均长度时,随着沟道长度的增加,器件开关比增加,光电流减小.相关研究结果为高纯碳纳米管薄膜晶体管器件在红外光探测器方面的进一步应用提供参考依据.     

Pt/纳米碳管空气电极氧还原反应的电催化性能

以不同质量比的铂、纳米碳管、活性炭为催化层制备空气电极并测定其稳态极化曲线和交流阻抗.研究发现,纳米碳管经硝酸处理后其氧还原反应性能得到提高,特别是将表面氧化后再沉积Pt,对氧的电还原反应影响更显著.以质量比4∶1的活性炭/纳米碳管载Pt制备的空气电极,在过电位ηc为500～600mV下,氧还原电流可达600～700mA·cm-2.EIS测试表明,纳米碳管载Pt后的欧姆极化阻抗和电化学阻抗均非常小.     

The effects of the lengths and orientations of single-walled carbon nanotubes on the electrochemistry of nanotube-modified electrodes

The influence of both nanotube orientation and length on the electrochemical properties of electrodes modified with single-walled carbon nanotubes was investigated. Gold electrodes were modified with either randomly dispersed or vertically aligned nanotubes to which ferrocenemethylamine was attached. Electron transfer kinetics were found to depend strongly on the orientation of the nanotube, with electron transfer between the gold electrode and the ferrocene moiety being 40 times slower through randomly dispersed nanotubes than through vertically aligned nanotubes. The difference is hypothesized to be due to electron transfer being more direct through a single tube than that with electrodes modified with randomly dispersed nanotubes. With the vertically aligned nanotubes the rate constant for electron transfer varied inversely with the mean length of the nanotubes. The results indicate there is an advantage in using aligned carbon nanotube arrays over randomly dispersed nanotubes for achieving efficient electron transfer to bound redox active species such as in the case of bioelectronic or photovoltaic devices.     

自组装半导体碳纳米管薄膜的光电特性

采用自组装的方法制备99%高纯度半导体碳纳米管平行阵列条带,以金属钯和钪为非对称接触电极制备碳纳米管（CNT）薄膜晶体管（TFTs）器件. 主要研究不同沟道长度碳纳米管薄膜晶体管器件的电输运特性和红外光电响应特性,分析了其中的载流子输运和光生载流子分离的物理机制. 我们发现薄膜晶体管器件的电学性能和光电性能依赖于器件沟道长度（L）和碳纳米管的平均长度（L_CNT）. 当沟道长度小于碳纳米管的平均长度时,器件开关比最低;当沟道长度超过碳纳米管平均长度时,随着沟道长度的增加,器件开关比增加,光电流减小.相关研究结果为高纯碳纳米管薄膜晶体管器件在红外光探测器方面的进一步应用提供参考依据.     

Selective Voltammetric Detection of Uric Acid in the Presence of Ascorbic Acid at Well‐Aligned Carbon Nanotube Electrode

The voltammetric behaviors of uric acid (UA) and L ‐ascorbic acid (L ‐AA) were studied at well‐aligned carbon nanotube electrode. Compared to glassy carbon, carbon nanotube electrode catalyzes oxidation of UA and L ‐AA, reducing the overpotentials by about 0.028 V and 0.416 V, respectively. Based on its differential catalytic function toward the oxidation of UA and L ‐AA, the carbon nanotube electrode resolved the overlapping voltammetric response of UA and L ‐AA into two well‐defined voltammetric peaks in applying both cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which can be used for a selective determination of UA in the presence of L ‐AA. The peak current obtained from DPV was linearly dependent on the UA concentration in the range of 0.2 μM to 80 μM with a correlation coefficient of 0.997. The detection limit (3δ) for UA was found to be 0.1 μM. Finally, the carbon nanotube electrode was successfully demonstrated as a electrochemical sensor to the determination of UA in human urine samples by simple dilution without further pretreatment.     

Molecular beam-controlled nucleation and growth of vertically aligned single-wall carbon nanotube arrays

The main obstacle to widespread application of single-wall carbon nanotubes is the lack of reproducible synthesis methods of pure material. We describe a new growth method for single-wall carbon nanotubes that uses molecular beams of precursor gases that impinge on a heated substrate coated with a catalyst thin film. In this growth environment the gas and the substrate temperature are decoupled and carbon nanotube growth occurs by surface reactions without contribution from homogeneous gas-phase reactions. This controlled reaction environment revealed that SWCNT growth is a complex multicomponent reaction in which not just C, but also H, and O play a critical role. These experiments identified acetylene as a prolific direct building block for carbon network formation that is an order of magnitude more efficient than other small-molecule precursors. The molecular jet experiments show that with optimal catalyst particle size the incidence rate of acetylene molecules plays a critical role in the formation of single-wall carbon nanotubes and dense vertically aligned arrays in which they are the dominant component. The threshold for vertically aligned growth, the growth rate, the diameter, and the number of walls of the carbon nanotubes are systematically correlated with the acetylene incidence rate and the substrate temperature.     

Synthesis of vertically aligned carbon nanotube arrays on polyhedral Fe/Al2O3 catalysts

Polyhedral Fe/Al(2)O(3) catalysts prepared by an impregnation method were used for the synthesis of vertically aligned carbon nanotube (CNT) arrays from the pyrolysis of ethylene at 800 °C.     

铁掺杂TiO2纳米管阵列制备及其光电化学性质

应用电化学阳极氧化法,以Fe(NO3)3-HF的混合水溶液作电解液在Ti基底上制备Fe掺杂TiO2纳米管阵列.FESEM、Raman、XPS、DRS等测试表明:经Fe掺杂的TiO2纳米管阵列,管径50~90 nm,管长约200nm.与未掺杂TiO2纳米管阵列相比,前者的紫外可见起始吸收带边随着Fe掺入量的增加而红移;而光电化学性质如光电流也随之显著提高.