Growth of millimeter-long and horizontally aligned single-walled carbon nanotubes on flat substrates

Millimeter-long and well-aligned single-walled carbon nanotubes (SWNTs) have been produced on silica/silicon surfaces using the carbon monoxide chemical vapor deposition (CO-CVD) method. The orientation of the nanotube arrays can be well-controlled by the gas flow during the growth. The majority of the orientated SWNTs are straight and individual. The length of the nanotubes can be >2 mm for a 10 min growth. Furthermore, multidimensional crossed-networks of SWNT can be easily generated by multistep processes. These results present a great opportunity in the controllable production of organized SWNT arrays for large-scale carbon nanotube-based nanodevice fabrication.     

Light-controlled single-walled carbon nanotube dispersions in aqueous solution

We have succeeded in dispersing single-walled carbon nanotubes (SWNTs) into an aqueous solution of poly(ethylene glycol)-terminated malachite green derivative (PEG-MG) through simple sonication. It was found that UV exposure caused reaggregation of these predispersed SWNTs in the same aqueous medium, as adsorbed PEG-MG photochromic chains could be effectively photocleavaged from the nanotube surface. The observed light-controlled dispersion and reaggragation of SWNTs in the aqueous solution should facilitate the development of SWNT dispersions with a controllable dispersity for potential applications.     

Improving dispersion and integration of single‐walled carbon nanotubes in epoxy composites by using a reactive noncovalent dispersant

Uniform dispersion and strong interfacial interaction are two critical prerequisites for application of single‐walled carbon nanotubes (SWNTs) in polymer composites. To endow the composites with multifunctional feature, no damage on the chemical/electronic structure of SWNTs is also usually required. With these ends in view, two epoxide‐containing pyrene derivatives (EpPys) were designed, synthesized, and used as reactive noncovalent dispersants for developing multifunctional epoxy/SWNT composites. One having longer chain length between epoxide group and pyrene moiety, that is, EpPy‐16, shows higher dispersing efficiency and provides the nanotube dispersion with better stability, thus picking up for subsequent studies. Systematic characterization on SWNT/EpPy‐16 hybrid demonstrates that 13.2 wt % of EpPy‐16 is adsorbed on the SWNT surface through strong π‐stacking interaction, and intrinsic electronic structure of SWNTs is basically reserved. The solution‐based process adopted here preserves the good SWNT dispersing state in dispersion into the composites. Simultaneously, enhanced interfacial interaction is also realized by using EpPy‐16, which interacts noncovalently with SWNT but connects covalently to epoxy network. As a result, the composites acquire 37 and 22% increments in tensile strength and Young's modulus, respectively, relative to that of neat resin. A low‐electrical percolation threshold of 0.1 wt % SWNTs and improved thermal properties were also observed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Identification of the structures of superlong oriented single-walled carbon nanotube arrays by electrodeposition of metal and Raman spectroscopy

In this Communication, we have demonstrated a facile and effective approach to identify the structure of the superlong well-aligned single-walled carbon nanotubes (SWNTs) by the combination of electrodeposition of metal (Ag) with Raman spectroscopy. The suitable density and the visibility of the Ag-deposited long oriented nanotubes make it possible to acquire Raman spectra from isolated individual nanotubes very easily. The results reveal that the well-oriented SWNT arrays on SiO2/Si wafer fabricated by EtOH chemical vapor deposition using Fe/Mo nanoparticles as catalyst exhibit a low percentage of metallic SWNTs (5%). Among other SWNTs about 62.3% are semiconducting SWNTs, and a small amount of nanotubes are quasimetallic. About 32% are a so-called quasi-insulator, which is caused inevitably by the defects during growth. Furthermore, the structural uniformity of the long SWNTs can be also evaluated by the deposition of Ag along the length and Raman spectroscopy. This method also provides an approach to deposit other metals on long SWNTs, which could have various potential applications such as for use as sensors, etc. More importantly, this facile method can be applied to long SWNT arrays fabricated from other different catalytic systems so that the relationship between the growth conditions and the structures of SWNTs are expected to be ruled out.     

Selective synthesis combined with chemical separation of single-walled carbon nanotubes for chirality selection

Single-walled carbon nanotubes (SWNTs) are potential materials for future nanoelectronics. Since the electronic and optical properties of SWNTs strongly depend on tube diameter and chirality, obtaining SWNTs with narrow (n,m) chirality distribution by selective growth or chemical separation has been an active area of research. Here, we demonstrate that a new, bimetallic FeRu catalyst affords SWNT growth with narrow diameter and chirality distribution in methane CVD. At 600 degrees C, methane CVD on FeRu catalyst produced predominantly (6,5) SWNTs according to UV-vis-NIR absorption and photoluminescence excitation/emission (PLE) spectroscopic characterization. At 850 degrees C, the dominant semiconducting species produced are (8,4), (7,6), and (7,5) SWNTs, with much narrower distributions in diameter and chirality than materials grown by other catalysts. Further, we show that narrow diameter/chirality growth combined with chemical separation by ion exchange chromatography (IEC) greatly facilitates achieving single (m,n) SWNT samples, as demonstrated by obtaining highly enriched (8,4) SWNTs with near elimination of metallic SWNTs existing in the as-grown material.     

铂粒子修饰单壁碳纳米管/聚苯胺复合膜对甲醛的电催化氧化

在溶有单壁碳纳米管(SWNTs)的苯胺溶液中, 通过电化学共聚合法成功制备了单壁碳纳米管(SWNT)/聚苯胺(PANI)复合膜. 用电沉积法将铂沉积到SWNT/PANI复合膜上. 样品的成分和形貌分别用XRD和SEM表征. 四探针和电化学交流阻抗的研究表明被PANI包裹的SWNTs整齐地排列在复合膜中, 从而提高了复合膜的电导率, 促进了电荷转移. 循环伏安(CV)说明Pt修饰的SWNT/PANI复合膜对于甲醛氧化具有良好的电催化活性及稳定性. 研究结果表明SWNT/PANI复合膜是一种非常好的催化剂载体, 有着广泛的应用前景.     

Electrochemical and conductivity measurements of single-wall carbon nanotube network electrodes

The electrochemical response of two-dimensional networks of pristine single-wall carbon nanotubes (SWNTs) has been investigated. SWNTs were grown by catalyzed chemical vapor deposition on an insulating SiO2 substrate, and then electrically contacted by lithographically defined Au electrodes. Subsequent insulation of the contact electrodes enabled the electrochemical properties of the SWNT network to be isolated and directly studied for the first time. The electrochemical activity of the SWNT network was found to be strongly dependent on the applied potential. For the same SWNT electrode, the limiting current for the oxidation of 5 mM Fe(phen)32+ was found to be much greater than expected based on the signal for the reduction of 5 mM Ru(NH3)63+. Simultaneous conductance and electrochemical measurements demonstrated decreasing conductance as the potential was scanned negative (versus Ag/AgCl) with the minimum conductance at around the reduction potential for Ru(NH3)63+. These results are consistent with the presence of both metallic and semiconducting SWNTs in the SWNT network electrode. Moreover, these results show that through appropriate choice of mediator and electrode potential, metallic SWNTs can be electrochemically addressed independently of semiconducting SWNTs.     

Direct Bioelectrocatalysis of PQQ‐Dependent Glucose Dehydrogenase

The direct bioelectrocatalysis was demonstrated for pyrroloquinoline quinone‐dependent glucose dehydrogenase (PQQ‐dependent GDH) covalently attached to single‐walled carbon nanotubes (SWNTs). The homogeneous ink‐like SWNT suspension was used for both creating the SWNT network on the microelectrode carbon surface and for enzyme immobilization. Functionalization of the SWNT surface by forming active ester groups was found to considerably enhance SWNT solubility in water with a range from 0.1 to 1.0 mg/mL. The PQQ‐dependent GDH immobilized on the surface of the SWNTs exhibited fast heterogeneous electron transfer with a rate constant of 3.6 s^?1. Moreover, the immobilized PQQ‐dependent GDH retained its enzymatic activity for glucose oxidation. A fusion of PQQ‐dependent GDH with SWNTs has a great potential for the development of low‐cost and reagentless glucose sensors and biofuel cells.     

Rheological, thermal, and mechanical characterizations of polystyrene/single-walled carbon nanotube composites

For preparation of polystyrene (PS) composites, a polymeric dispersant, pyrene-capped polystyrene (PyPS), was applied for noncovalent functionalization of single-walled carbon nanotubes (SWNTs) to improve both dispersion quality and PS–SWNT interfacial interactions. To demonstrate the critical role of PyPS, the composites with the absence of PyPS (PS/SWNT) were also prepared for comparison. Rheological studies suggest that addition of SWNTs, particularly of PyPS-functionalized SWNTs, suppresses significantly large-scale relaxation of PS chains but has little effect on their short-range dynamics. Relative to PS, moderately improved thermal and mechanical properties took place on the composites with either pristine or PyPS-functionalized SWNTs. The PS/PyPS/SWNT composite usually presents better performance than the PS/SWNT one at a fixed SWNT content.     

Experimental and Computational Investigations of the Properties of Fluorinated Single‐Walled Carbon Nanotubes

Fluorination of single‐walled carbon nanotubes by reaction with elemental fluorine at elevated temperatures provides fluorinated single‐walled carbon nanotubes (F‐SWNT), which have the highest degree of functionalization (up to F/C=1/2) of any derivatized carbon‐nanotube material reported to date. Also, F‐SWNTs have received more scrutiny than any other functionalized carbon nanotubes. This Minireview covers experimental and computational investigations of F‐SWNTs with a focus on the nature and the strength of the C–F linkage.     

The radiation degradation of a nanotube-polyimide nanocomposite

The radiation degradation of a nanotube-polyimide nanocomposite was studied. Radiation chemistry was observed that was not present in the unmodified polymer or in the imbedded single-walled carbon nanotubes (SWNTs) themselves. The tensile properties were found to be improved by the addition of SWNTs in the unirradiated materials, and no deterioration in these properties with irradiation was observed. The SWNTs were found to have a detrimental effect on the optical properties however. The transparency of the composite was degraded significantly faster by electron-beam radiation than the neat polymer was. This may make the SWNT/polyimide composites unsuitable for some space applications. Electron Spin Resonance (ESR) measurements determined that the SWNTs interfere with the radical chemistry in the irradiated materials. This could be due to energy dissipation by the SWNT network, preventing the formation of radical species, or alternatively, preferential reaction or termination of radicals by the nanotubes. FT-Raman spectroscopy was found to be a very useful tool for examining SWNTs embedded at low concentrations. It revealed no signs of SWNT degradation up to 10 MGy.     

High dispersion and electrocatalytic properties of palladium nanoparticles on single-walled carbon nanotubes

Palladium (Pd) nanoparticles were electrochemically dispersed on single-walled carbon nanotubes (SWNTs) by electroreduction of octahedral Pd(IV) complex formed on the SWNT surface. The structure and nature of the resulting Pd-SWNT composites were characterized by transmission electron microscopy and X-ray diffraction. The electrocatalytic properties of the Pd/SWNT electrode for hydrazine oxidation have been investigated by cyclic voltammetry; high electrocatalytic activity of the Pd/SWNT electrode can be observed. This may be attributed to the high dispersion of palladium catalysts and the particular properties of SWNT supports. The results imply that the Pd-SWNT composite has good potential applications in fuel cells.     

Synergistically Enhanced Dispersion of Native Protein–Carbon Nanotube Conjugates by Fluoroalcohols in Aqueous Solution

Carbon nanotubes (CNTs) are anticipated as an important new material for use in nanotechnology applications because of their excellent mechanical and electrical properties. For their development, a highly stable dispersion of debundled CNTs is indispensable. Herein we present a new method to enhance dispersibility of single‐walled carbon nanotubes (SWNTs) with proteins using alcohols as co‐solvents. Addition of fluoroalcohols in solution increased the SWNT dispersion by more than one order of magnitude without protein denaturation. Enhancement of SWNT dispersion through addition of alcohols was attributed to the decreased hydrophobic interaction among SWNTs. This novel approach enables us to produce biofunctional CNTs such as one‐dimensional nanobiosensors and drug carriers that can penetrate cells.     

Electorchemical Studies of Cytochrome c on Electodes Modified by Single—Wall Carbon Naotubes

Single-wall carbon nanotubes(SWNTs) modified gold electrodes were prepared by using two different methods.The electrochemical behavior of cytochrome c on the modified gold electrodes was investigated.The first kind of SWNT-modified electrode (noted as SWNT/Au electrode)was prepared by the adsorption of carboxylterminated SWNTs from DMF dispersion on the gold electrode.The oxidatively processed SWNT tips were covalently modified by coupling with amines (AET) to form amide linkage.Via Au-S chemical bonding,the self-assembled monolayer of thiol-unctionalized nanotubes on gold surface was fabricated so as to prepare the others SWNT-modified electrode (noted as SWNT/AET/Au electrode).It was shown from cyclic voltammetry cxperiments that cytochrome c exhibited direct electrochemical responses on the both electrodes, but only the current of controlled diffusion existed on the SWNT/Au electrode while both the currents of controlled diffusion and adsorption of cytochrome c occurred on the SWNT/AET/Au electrode.Photoelastic Modulation Infared Reflection Absorpthion Spectroscopy (PEM-IRRAS) and Quartz Crystal Microbalance (QCM) were employed to verify the adsorption of SWNTs on the gold electrodes.The results proved that SWNTs could enhance the direct electron transfer proecss between the electrodes and redox proteins.     

Nano-crystalline FeOOH mixed with SWNT matrix as a superior anode material for lithium batteries

Nano-crystalline FeOOH particles(5～10 nm) have been uniformly mixed with electric matrix of single-walled carbon nanotubes(SWNTs)for forming FeOOH/SWNT composite via a facile ultrasonication method. Directly using the FeOOH/SWNT composite(containing 15 wt%SWNTs) as anode material for lithium battery enhances kinetics of the Li+insertion/extraction processes, thereby effectively improving reversible capacity and cycle performance, which delivers a high reversible capacity of 758 mAh g-1under a current density of 400 mA g-1even after 180 cycles, being comparable with previous reports in terms of electrochemical performance for FeOOH anode. The good electrochemical performance should be ascribed to the small particle size and nano-crystalline of FeOOH, as well as the good electronic conductivity of SWNT matrix.     

Ultrathin "bed-of-nails" membranes of single-wall carbon nanotubes

Single-wall carbon nanotubes (SWNTs) were arranged in a membrane similar to a "bed-of-nails", in which a single layer of parallel SWNTs was densely packed and aligned along the normal to the membrane. The planar, free-standing, ultrathin SWNT membranes were prepared by milling a neat SWNT fiber with a gallium focused ion beam. The approach is readily applicable to cutting nanotubes to a desirable and precise length and enables further fabrication of devices using the "bed-of-nails" membranes to test the transport properties of SWNTs.     

Metal-enhanced fluorescence of carbon nanotubes

The photoluminescence (PL) quantum yield of single-walled carbon nanotubes (SWNTs) is relatively low, with various quenching effects by metallic species reported in the literature. Here, we report the first case of metal enhanced fluorescence (MEF) of surfactant-coated carbon nanotubes on nanostructured gold substrates. The photoluminescence quantum yield of SWNTs is observed to be enhanced more than 10-fold. The dependence of fluorescence enhancement on metal-nanotube distance and on the surface plasmon resonance (SPR) of the gold substrate for various SWNT chiralities is measured to reveal the mechanism of enhancement. Surfactant-coated SWNTs in direct contact with metal exhibit strong MEF without quenching, suggesting a small quenching distance for SWNTs on the order of the van der Waals distance, beyond which the intrinsically fast nonradiative decay rate in nanotubes is little enhanced by metal. The metal enhanced fluorescence of SWNTs is attributed to radiative lifetime shortening through resonance coupling of SWNT emission to the reradiating dipolar plasmonic modes in the metal.     

A Computational Study of a Single‐Walled Carbon‐Nanotube‐Based Ultrafast High‐Capacity Aluminum Battery

Exploring suitable electrode materials is a fundamental step toward developing Al batteries with enhanced performance. In this work, we explore using density functional theory calculations the feasibility of single‐walled carbon nanotubes (SWNTs) as a cathode material for Al batteries. Carbon nanotubes with hollow structures and large surface area are able to overcome the difficulty of activating the opening of interlayer spaces as observed in graphite electrode during the first intercalation cycle. Our results show that AlCl₄ binds strongly with the SWNT to result in an energetically and thermally stable AlCl₄‐adsorbed SWNT system. Diffusion calculations show that the SWNT system allows ultrafast diffusion of AlCl₄ with a more favorable inner surface diffusion than outer surface diffusion. Our charge‐density difference and Bader atomic charge analysis confirm the oxidation of SWNT upon adsorption of AlCl₄, which shows a similar behavior to the previously studied graphite cathode. The average open‐circuit voltage and AlCl₄ storage capacity increases with increasing SWNT diameter and can be as high as 1.96 V and 275 mA h g⁻¹ in (25,25) SWNT relative to graphite (70 mA h g⁻¹). All of these properties show that SWNTs are a potential cathode material for high‐performance Al batteries and should be explored further.     

Antenna chemistry with metallic single-walled carbon nanotubes

We show that, when subjected to microwave fields, surfactant-stabilized single-walled carbon nanotubes (SWNTs) develop polarization potentials at their extremities that readily drive electrochemical reactions. In the presence of transition metal salts with high oxidation potential (e.g., FeCl3), SWNTs drive reductive condensation to metallic nanoparticles with essentially diffusion-limited kinetics in a laboratory microwave reactor. Using HAuCl4, metallic particles and sheaths deposit regioselectively at the SWNT tips, yielding novel SWNT-metal composite nanostructures. This process is shown to activate exclusively metallic SWNTs; a degree of diameter selectivity is observed using acceptors with different oxidation potentials. The reaction mechanism is shown to involve Fowler-Nordheim field emission in solution, where electric fields concentrate at the SWNT tips (attaining approximately 10(9) V/m) due to the SWNT high aspect ratio (approximately 1000) and gradient compression in the insulating surfactant monolayer. Nanotube antenna chemistry is remarkably simple and should be useful in SWNT separation and fractionation processes, while the unusual nanostructures produced could impact nanomedicine, energy harvesting, and synthetic applications.