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.     

Electrooxidation of hydrazine catalyzed by noncovalently functionalized single-walled carbon nanotubes with CoPc

We report on the electrooxidation of hydrazine catalyzed by single-walled carbon nanotube (SWCNT) functionalized with cobalt phthalocyanine (CoPc) which shows that the presence of the single-walled carbon nanotubes enhances the catalytic activity of the CoPc itself without any change in the reaction mechanism. A synergistic effect, in terms of reactivity when the new nanocomposite material was adsorbed on the GC electrode, was observed. The obtained hybrid electrodes were tested under hydrodynamic conditions, showing two different oxidation processes, which suggest the presence of two different types of active sites on the electrode surface catalyzing the reaction. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)₆]^3−/4− as a redox probe revealed that the GC/SWCNT + CoPc showed much lower electron-resistance (R_et) confirming the synergistic effect of the composite mentioned above. Atomic force microscopy (AFM) images showed the clear differences in surface roughness for each film, confirming the different compositions of the hybrid electrodes used in this study.     

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.     

Effect of catalyst combination on growth of single-walled carbon nanotubes

A new effective catalysts combination of iron — nickel for alcohol CVD technique was found. This catalyst catalyzed well as well as the typical catalyst of iron — cobalt catalysts, but gave a different diameter distribution. Calculating their electrical density of states under the assumption of their solid lattice structures, the result was fairly consistent with experimental results. The number of electrical states near Fermi level that is considered to be important for catalytic reaction is enough and the DOS of iron – nickel catalyst was quite similar to that of cobalt unlike manganese – copper catalyst. Consequently, a blend of catalysts that has a similar DOS to cobalt and has enough states near the Fermi level can be a good catalyst for alcohol CVD.     

Chiral-selective growth of single-walled carbon nanotubes on stainless steel wires

Single-walled carbon nanotubes (SWCNTs) were successfully grown on calcined stainless steel wires at 700 °C using CO as the carbon source. By contrast, the raw stainless steel wires produced only necklace-like multi-walled carbon nanotubes. Photoluminescence spectroscopy studies showed that SWCNTs grown from calcined stainless steel have a narrow diameter distribution and a high chiral selectivity of (6,5) nanotubes. The pre-growth heat treatment of the stainless steel leads to formation of iron and chromium oxides. The reduction of iron oxide results in formation of Fe nanoparticles which, anchored by chromium oxide, account for the chiral-selective growth of SWCNTs.     

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.     

Promotion of cell growth with magnetically enhanced single-walled carbon nanotubes

We demonstrate that purified and functionalized single walled carbon nanotubes (SWNTs) promote the growth of NIH3T3 mouse fibroblast cells under a magnetic field. The SWNTs are functionalized in acidic solutions by attaching carboxyl groups (–COOH) on their surfaces. Functionalized SWNTs (fSWNTs) exhibit a ferromagnetic property when dispersed in water. Cytotoxicity after the delivery of the fSWNTs into the cells is significantly reduced due to the complete removal of toxic metallic impurities during the functionalization process. The efficient uptake of the fSWNTs by the cells is confirmed through transmission electron microscopy (TEM). It is discovered that the growth of the NIH3T3 cells treated with the fSWNTs is enhanced by up to 25% than control cells when an external magnetic field is applied. Our findings may lead to the non-invasive and non-toxic drug delivery as well as targeted cell therapy with fSWNTs.     

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.     

Lattice-directed growth of single-walled carbon nanotubes with controlled geometries on surface

How to control the orientations of single-walled carbon nanotubes (SWCNTs) on surface is the key point to controlling their geometries. In this work, we chose quartz (0 0 1), MgO (0 0 1) and layered mica with 3-, 4- and 6-fold symmetry, respectively as substrates to grow SWCNTs using gas-flow and lattice-directed modes. The produced SWCNTs were aligned along the symmetrical directions and displayed the homologous angles of 120°, 90° and 60° during growth on quartz (0 0 1), MgO (0 0 1) and mica surfaces, respectively. The obtained SWCNTs with controlled geometries would have wide applications in nanoelectronic devices in the future.     

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.     

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.     

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。     

Lateral growth of single-walled carbon nanotubes across electrodes and the electrical property characterization

To realize the commercialization of single-walled carbon nanotube (SWNT)-based nanoelectronic and optoelectronic devices, the development of a fabrication process of catalytic chemical vapour deposition (CCVD) growth of SWNTs across electrodes is required. In this work, we report on the process of the lateral growth of SWNTs across catalytic pads. Using the conventional photolithography technique followed by thin film evaporation and lift off, the catalytic pads were prepared, consisting of nickel (Ni) and silicon dioxide (SiO₂) double layers, on the thermal silicon oxide substrate. The SWNTs were laterally grown across the catalytic pads in a thermal pyrolysis CVD system at 800–900 °C fed with a mixed gas flow of methane (CH₄) and hydrogen (H₂). The SiO₂, as the upper layer on Ni pads, not only plays a role as a barrier to prevent vertical growth but also serves as a porous medium that helps in forming smaller nano-sized Ni particles, so that the use of ultrathin Ni film would not be necessary for growth of SWNTs. Lateral growth across pads of various inter-spacing up to tens of microns was conducted for devices of different applications. The characterization by micro-Raman spectroscopy, atomic force microscopy and electron microscopy revealed the structure and diameters of the SWNTs and most importantly the SWNT density controlled by changing growth temperature. Following SWNTs growth, post-definition of metallic electrodes was conducted and the electrical properties were also measured.     

Co-Mo catalyzed growth of multi-wall carbon nanotubes from CO decomposition

We investigated the growth of multi-wall carbon nanotubes (CNTs) catalyzed by SiO₂-supported Co-Mo bi-metallic catalyst in flowing CO at 700 °C. We found that both Co and Mo are present in catalytic particles at the tips of CNTs, but their compositions vary from one catalytic particle to another and significantly deviate from the initial mixing composition. The Co concentration and distribution in the catalytic particle of a CNT largely determines the length of the CNT. The CNT growth process is carbon adsorption on exposed area of a catalytic particle and subsequent precipitation at the CNT-catalyst interface or open CNT wall edges. The encapsulation of a catalytic particle was found to occur by the growth of the open-edged graphene walls around the particle. Two types of long CNTs were observed: one with their CNT walls ended at the CNT-particle interface, and the other with their CNT walls open to the environment. The former have diameters similar to their catalytic particle size while the latter have larger diameters.     

CVD catalytic growth of single-walled carbon nanotubes with a selective diameter distribution

Thermal pyrolysis chemical vapor deposition growth of single-walled carbon nanotubes (SWNTs) was demonstrated by using catalytic pads of nickel (3∼4 nm) and SiO₂ (100 nm) deposited by electron-beam evaporation in sequence on the thermal silicon oxide substrate. The diameters of SWNTs on the samples with upper SiO₂ layer of different deposition rates were characterized by atomic force microscopy (AFM) and micro-Raman spectroscopy. It was observed that the average diameter and density of SWNTs increased as the deposition rate of upper SiO₂ layer increased. The differences of the SWNTs diameter distribution were attributed to the differences in the curvature of the SiO₂ porous structure deposited with different deposition rates. The high-resolution transmission electron micrographs and the corresponding diffractogram showed that SWNTs with diameter as low as 0.51 nm could be found and the AFM measurements revealed that a high percentage (∼ 70%) of SWNTs of diameters lower than 1.0 nm was achieved by upper SiO₂ layer deposition rate of 0.5 Å/s, whereas bundles of SWNTs were found with higher SiO₂ deposition rates.     

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.