Ferrocene-filled single-walled carbon nanotubes

Ferrocene molecules are successfully introduced into the inner hollow space of Single-walled carbon nanotubes (SWNTs) to get ferrocene-filled SWNTs (Fc@SWNTs). This nanohybrid material was carefully characterized by high resolution microscopy, FTIR spectrum, and Cyclic voltammetry (CV). This new material may not only act as air stable n-type field-effect transistors based on nanotubes, but it may also be employed as building blocks for various devices based on the redox activity of ferrocene. What’s more, upon high temperature annealing, the encapsulated ferrocene molecules will decompose and change into interior tubes, forming double-walled carbon nanotubes (DWNTs). This provides convincing evidence that ferrocene molecules are inserted into the hollow cavities SWNTs. This result also presented a controllable way to synthesize DWNTs.     

Theoretical studies on the charge-induced failure of single-walled carbon nanotubes

Electromechanical coupling in single-walled carbon nanotubes has been studied theoretically. The charge distribution on single-walled carbon nanotubes in an electric field is obtained by an atomistic moment method based on classical electrostatics theory. The electrostatic interactions between charged carbon atoms are calculated using the Coulomb law. The charge-induced deformations of single-walled carbon nanotubes in axial and radial directions are obtained by using the molecular structural mechanics method and considering the electrostatic interactions as external loads acting on carbon atoms. The electrical failure of charged carbon nanotubes is found to be controlled by the charge level and also affected by the caps on the nanotube ends. The results indicate that the bond breaking first appears at the tube ends and the end-caps can enhance the stability of the nanotubes.     

Chemistry of single-walled carbon nanotubes

In this Account we highlight the experimental evidence in favor of our view that carbon nanotubes should be considered as a new macromolecular form of carbon with unique properties and with great potential for practical applications. We show that carbon nanotubes may take on properties that are normally associated with molecular species, such as solubility in organic solvents, solution-based chemical transformations, chromatography, and spectroscopy. It is already clear that the nascent field of nanotube chemistry will rival that of the fullerenes.     

Formylation of single-walled carbon nanotubes

Formyl or aldehyde groups are transferred to the surface of single-walled carbon nanotubes (SWCNTs) by reaction of reduced carbon nanotubes with N-formylpiperidine. This could open the way for more versatile chemical modification reactions of carbon nanotubes than is currently possible using functionalization methods reported to date. The formylated SWCNTs were characterized by thermogravimetric analysis-mass spectrometry and Raman, UV-vis-NIR and FTIR spectroscopy. The location and distribution of the functional groups was determined by AFM using electrostatic interactions with gold nanoparticles. The formylated SWCNTs were further derivatized with a fluorescent dye and studied using fluorescence spectroscopy.     

Trial for diameter-selective synthesis of single-walled carbon nanotubes

The diameter-controlled synthesis of single-walled carbon nanotubes (SWNTs) has been examined experimentally. The catalysis of the Rh and Pd atoms has been confirmed by blending with Co atoms at 950 °C in a furnace, although the Rh/Pd catalyst has not been recorded to act efficiently at this temperature before. Raman spectra indicate that the Rh/Co and Pd/Co catalysts can synthesize narrow-diameter SWNTs more selectively than the Fe/Co and Ni/Co catalysts, which can only synthesize SWNTs with slightly larger diameters. These results suggest that by changing the combination of catalysts, the persistent problem of controlling the diameter of SWNTs can be solved without any expensive setup or complicated techniques.     

Prediction of elastic properties for single-walled carbon nanotubes

Based on a link between molecular and solid mechanics, an analytical method was developed for modeling the elastic properties of single-walled carbon nanotubes (SWNTs). A SWNT is regarded as a continuum-shell model which is composed of the discrete molecular structures linked by the carbon-to-carbon bonds. The elastic properties were investigated for the SWNTs as a function of the nanotube size in terms of the chiral vector integers (n,m). The theoretical prediction on elastic properties agreed reasonably with the existing experiment and theoretical results. The present formulas are able to serve as a good approximation of the elastic properties for SWNTs.     

Torsional behavior of single-walled carbon nanotubes

Atomistic simulations were performed to investigate the deformation behavior of single-walled carbon nano-tubes (SWCNTs) under torsional loading. The evolutions of the potential energy and stresses were presented. Radial distribution functions (RDFs) were calculated to analyze structural evolution during torsional deformation. The results show that during torsion, the tensile stress component along the tube axis is most significant and other stress components are almost negligible. The tensile stress stretched the C–C bonds until they reached the bond length of 0.18 nm. The torsional strength of the SWCNTs is about 30% of the tensile strength. Buckling took place at a few degrees of torsional angle and propagated along the tube as the torsional angle increased, and collapse of the tube wall followed buckling. These structural evolutions can be well described with the RDFs. Two new peaks appeared at 0.21 nm and 0.18 nm in the RDFs, corresponding to the minimum spacing between the atoms in the collapsed layers, and the maximum bond length that can be reached in stretching before rupture.     

单壁碳纳米管分离研究

根据导电性能不同,单壁碳纳米管可以分为金属型和半导体型。目前所有方法制备的单壁碳纳米管,其产物为金属型和半导体型单壁碳纳米管的混合物,且很难将它们分开,这极大地阻碍了单壁碳纳米管在很多领域的应用。本文介绍了单壁碳纳米管的结构与导电性能的关系,着重综述了最新金属型和半导体型单壁碳纳米管的分离方法。     

Photophysics of individual single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are cylindrical graphitic molecules that have remained at the forefront of nanomaterials research since 1991, largely due to their exceptional and unusual mechanical, electrical, and optical properties. The motivation for understanding how nanotubes interact with light (i.e., SWNT photophysics) is both fundamental and applied. Individual nanotubes may someday be used as superior near-infrared fluorophores, biological tags and sensors, and components for ultrahigh-speed optical communications systems. Establishing an understanding of basic nanotube photophysics is intrinsically significant and should enable the rapid development of such innovations. Unlike conventional molecules, carbon nanotubes are synthesized as heterogeneous samples, composed of molecules with different diameters, chiralities, and lengths. Because a nanotube can be either metallic or semiconducting depending on its particular molecular structure, SWNT samples are also mixtures of conductors and semiconductors. Early progress in understanding the optical characteristics of SWNTs was limited because nanotubes aggregate when synthesized, causing a mixing of the energy states of different nanotube structures. Recently, significant improvements in sample preparation have made it possible to isolate individual nanotubes, enabling many advances in characterizing their optical properties. In this Account, single-molecule confocal microscopy and spectroscopy were implemented to study the fluorescence from individual nanotubes. Single-molecule measurements naturally circumvent the difficulties associated with SWNT sample inhomogeneities. Intrinsic SWNT photoluminescence has a simple narrow Lorentzian line shape and a polarization dependence, as expected for a one-dimensional system. Although the local environment heavily influences the optical transition wavelength and intensity, single nanotubes are exceptionally photostable. In fact, they have the unique characteristic that their single molecule fluorescence intensity remains constant over time; SWNTs do not "blink" or photobleach under ambient conditions. In addition, transient absorption spectroscopy was used to examine the relaxation dynamics of photoexcited nanotubes and to elucidate the nature of the SWNT excited state. For metallic SWNTs, very fast initial recovery times (300-500 fs) corresponded to excited-state relaxation. For semiconducting SWNTs, an additional slower decay component was observed (50-100 ps) that corresponded to electron-hole recombination. As the excitation intensity was increased, multiple electron-hole pairs were generated in the SWNT; however, these e-h pairs annihilated each other completely in under 3 ps. Studying the dynamics of this annihilation process revealed the lifetimes for one, two, and three e-h pairs, which further confirmed that the photoexcitation of SWNTs produces not free electrons but rather one-dimensional bound electron-hole pairs (i.e., excitons). In summary, nanotube photophysics is a rapidly developing area of nanomaterials research. Individual SWNTs exhibit robust and unexpectedly unwavering single-molecule fluorescence in the near-infrared, show fast relaxation dynamics, and generate excitons as their optical excited states. These fundamental discoveries should enable the development of novel devices based on the impressive photophysical properties of carbon nanotubes, especially in areas like biological imaging. Many facets of nanotube photophysics still need to be better understood, but SWNTs have already proven to be an excellent starting material for future nanophotonics applications.     

Electron-induced cutting of single-walled carbon nanotubes

Electron beam irradiation with moderate fluences of approximately 10¹⁶-10¹⁷ electrons per cm² is used for controllable, bulk-scale cutting of single-walled carbon nanotubes (SWCNTs). The effectiveness of high energy electron irradiation in cutting SWCNTs is dependent on the nature of the sidewall. While pristine nanotubes are very stable under irradiation conditions, ozonated SWCNTs combined with a moderate fluence of electrons resulted in bulk-scale cutting of nanotubes. The length distribution of the cut SWCNTs could be controlled by adjusting the irradiation fluence. The average length of the cut nanotubes was 65 nm with 85% of the nanotubes shorter than 100 nm.     

Pyrene-functionalised single-walled carbon nanotubes for mediatorless dioxygen bioelectrocatalysis

We have prepared electrodes for bioelectrocatalytic dioxygen reduction modified with single-walled carbon nanotubes non-covalently functionalised with 1-pyrenesulfonic acid, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid or 1-pyrenemethylamine. The nanotubes were immobilised in a hydrophilic or hydrophobic silicate matrix on tin-doped indium oxide and bilirubin oxidase was either adsorbed from solution or co-immobilised with the nanotubes in the silicate matrix. In the cases where the oxidase was absorbed from solution the charge of the functionalised nanotubes was decisive for the efficiency of the bioelectrocatalytic reduction of oxygen; very low electrocatalytic current was measured with positively charged pyrene functionalisation. In the case of co-immobilised enzyme the sign of the charge of the functional group has no effect on the catalytic efficiency of the modified electrodes. Rotating disk experiments show that the main limitation of the catalytic current is the supply of oxygen to the enzyme.The PSA-functionalised SWCNT electrodes were used as a cathode in zinc-oxygen battery.     

Electrical conductivity of well-exfoliated single-walled carbon nanotubes

Aqueous suspensions of single-walled carbon nanotubes (SWCNTs) with controlled degree of exfoliation were used to prepare conductive thin films. Controlled exfoliation was achieved by physical separation of SWCNT bundles using our previously established nanoplatelet-dispersion method. Thin film networks of individual SWCNTs produced with this approach exhibit universal conduction behavior indicative of an isotropic network of random resistors with nearly monodisperse bond conductance distribution. Networks made of partially exfoliated SWCNTs experience a significant shift in percolation threshold because of effective local alignment of individual SWCNTs into bundles. Bundling increases the conductivity of the SWCNTs at higher concentration because of low contact resistance electron transport between metallic SWCNTs. The most significant impact of bundling is the development of non-universal electrical scaling. These findings suggest that while individually exfoliated SWCNTs should be of substantial importance for electrical devices requiring small increases in electrical conductivity at low concentration, adequate control of bundling may enable or enhance performance for applications requiring higher conductivity.     

Physisorption of hydrogen in single-walled carbon nanotubes

The interaction of hydrogen with single-walled carbon nanotubes (SWNTs) was analysed. A SWNT sample was exposed to D₂ or H₂ at a pressure of 2 MPa for 1 h at 298 or 873 K. The desorption spectra were measured by thermal desorption spectroscopy (TDS). A main reversible desorption site was observed throughout the range 77 to 320 K. The activation energy of this peak at about 90 K was calculated assuming first-order desorption. This corresponds to physisorption on the surface of the SWNTs (19.2±1.2 kJ/mol). A desorption peak was also found for multi-walled carbon nanotubes (MWNTs), and also for graphite samples. The hydrogen desorption spectrum showed other small shoulders, but only for the SWNT sample. They are assumed to originate from hydrogen physisorbed at sites on the internal surface of the tubes and on various other forms of carbon in the sample. The nanosized metallic particles (Co:Ni) used for nanotube growth did not play any role in the physisorption of molecular hydrogen on the SWNT sample. Therefore, it is concluded that the desorption of hydrogen from nanotubes is related to the specific surface area of the sample.     

Nonlocal material properties of single-walled carbon nanotubes

Natural frequencies of single-walled carbon nanotubes (SWCNTs) obtained using a model based on Eringen's nonlocal continuum mechanics and the Timoshenko beam theory are compared with those obtained by molecular dynamics simulations. The goal was to determine the values of the material constant, considered here as a nonlocal property, as a function of the length and the diameter of SWCNTs. The present approach has the advantage of eliminating the SWCNT thickness from the computations. A sensitivity analysis of natural frequencies to changes in the nonlocal material constant is also carried out and it shows that the influence of the nonlocal effects decreases with an increase in the SWCNT dimensions. The matching of natural frequencies shows that the nonlocal material constant varies with the natural frequency and the SWCNT length and diameter.     

Magnetic-field-induced diameter-selective synthesis of single-walled carbon nanotubes

We report a facile and scalable approach to synthesize single-walled carbon nanotubes (SWNTs) with selected diameter distribution by applying a magnetic field perpendicular to the electric field in the arc plasma region. It is found that this magnetic field-induced diameter-selectivity strategy enables the control of the SWNTs with different diameter distributions in different regions, and the diameter-selective efficiency could be enhanced by modifying the direction of magnetic field. Our results indicate that the motions of the catalysts with different particle sizes, positive carbon ions and electrons are significantly influenced by the magnetic field and electromagnetic force, resulting in the different nucleation and growth processes of SWNTs due to the collective interactions between the magnetic field and arc plasma. This approach would enable a viable route towards the synthesis of SWNTs with desired diameter through the tuning of arc parameters in the arc discharge process.     

Selective oxidation of single-walled carbon nanotubes using carbon dioxide

A simple process for selective removal of carbon from single-walled carbon nanotube samples was developed based on a mild oxidation by carbon dioxide. The reactivity profiles of as prepared and purified nanotube samples were determined using both TG and a related analytical technique, controlled atmosphere programmed temperature oxidation (CAPTO). The complex differential rate curves for weight loss (DTG) or carbon dioxide evolution (CAPTO) could be resolved by a series of Gaussian peaks each associated with carbonaceous species of different reactivity. Comparisons were made between samples as received after preparation by the laser ablation method, after purification by nitric acid oxidation, and both of these after reaction with CO₂. The DTG of as prepared tubes had a broad major peak centered about 410 °C. Mild oxidation of as prepared nanotubes under flowing carbon dioxide at 600 °C preferentially removed more reactive carbon species leaving behind a narrower distribution about the major peak in DTG. In contrast to the as prepared material, the sample that had been purified using nitric acid had a more distinct separation of the major DTG peaks between more and less readily oxidized material. Oxidation of this sample with CO₂ selectively removed the peak associated with the most readily oxidized material. The original CO₂ oxidation experiments performed on the analytical scale were successfully scaled up to a small preparative scale.     

Characterizing single-walled carbon nanotubes by pressure probe

We compare the behavior of bond lengths, cross sectional shape and bulk modulus at ambient conditions and under hydrostatic pressure of all the three kinds of long uncapped single-walled carbon nanotubes. Results show that two bond lengths completely describe the structure of armchair and zigzag tubes (non-chiral), whereas only one bond length is required to define structure of chiral tubes. In armchair tubes, one bond length is found to be larger and the other smaller than the value for graphene, while in zigzag tubes one of the bond lengths remains equal to and the other larger than graphene bond length. In chiral tubes, three bond lengths are found to be equal to each other and their value depends on the chirality. At some critical pressure values depending on radius, both bond lengths become equal to each other in non-chiral tubes. Above these critical pressure values, the cross section shape changes from circular to oval and the pattern of bond lengths becomes different and dependent on the chirality of the tubes.