Synthesis of single-walled carbon nanotubes using hemoglobin-based iron catalyst

Hemoglobin (Hb) was used as a catalyst for the growth of single-walled carbon nanotubes (SWCNTs). Hb was deposited onto a hydrophilic treated substrate by spin coating method. After oxidation at 800 °C, protein chains were decomposed and iron oxide nanoparticles remained with an average diameter of 2.29 nm. High quality SWCNTs were synthesized with an average diameter of 1.22 nm. The protein chains prevent iron atoms aggregation and so the size of the nanoparticles is smaller than that from ferritin-like proteins.     

High-efficient synthesis of double-walled carbon nanotubes by arc discharge method using chloride as a promoter

With trace halide as a promoter in an iron sulfide catalyst, relatively perfect structural integrity double-walled carbon nanotubes (DWNTs) have been synthesized in large quantity and high yield by arc discharge method. Scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy were used for structural characterization and yield determination. The results revealed that halide was a crucial factor for selectively synthesizing high yield DWNTs. The detailed experimental parameters were systematically investigated. The possible role of halide in growth of DWNTs was discussed as well.     

Functionalization of single-walled carbon nanotubes by using alkyl-halides

In this paper we demonstrate the functionalization of single-walled carbon nanotubes prepared by chemical vapor deposition. The chosen functionalization agents were alkyl-halides such as trifluoromethane (TFM) and trichloromethane (TCM); or double bond containing alkyl-halides as tetrachloroethylene (TCE) and hexafluoropropene (HFP) that can easily form radicals. Functionalization of samples was carried out under mild conditions, by ball milling of nanotubes in an atmosphere of functionalization agent, at room temperature. For the sake of comparison, chlorination was also performed by chlorine gas. In this process the cleavage of nanotube C-C bonds results in active sites, which can activate molecules in gas phase or adsorbed on the surface of carbon nanotubes. Halogenated samples were characterized by means of particle induced γ-ray emission, transmission electron microscopy, thermogravimetry, and X-ray photoelectron spectroscopy. We concluded that this method gives functionalized single-walled carbon nanotubes in the range of 0.3-3.5 wt.% of fluorine and 5.5-17.5 wt.% of chlorine.     

Synthesis of water-soluble single-walled carbon nanotubes by RAFT polymerization

Water-soluble single-walled carbon nanotubes (SWNTs) were synthesized by grafting poly(acrylamide) (PAM) from the surface of SWNT via reversible addition-fragmentation chain transfer (RAFT) polymerization. The RAFT agents were covalently attached to the SWNTs by functionalizing SWNTs with in situ generated diazonium compounds. The product was characterized by means of FT-IR, Raman, ¹H NMR, TGA and TEM. The results showed that PAM chains had successfully grafted from SWNT by RAFT polymerization. The amount of PAM grown from SWNT increased with the polymerization time. The acrylamide conversion increased linearly with the polymerization time, indicating the “living” characteristics of the RAFT polymerization. TEM was utilized to image PAM-g-SWNT, showing relatively uniform polymer coatings present on the surface of individual, debundled nanotubes.     

A comprehensive scenario for commonly used purification procedures of arc-discharge as-produced single-walled carbon nanotubes

The purification of single-walled carbon nanotube (SWCNT) samples was analysed using a multi-technique approach, with structural as well as spectroscopic probes, in order to characterize the samples and to identify important factors for improvement of SWCNT sample quality. The first dry oxidation step (air at 365 °C) is shown to have only a weak selectivity for the removal of the amorphous carbon or weakly organized graphitic species as well as resulting in a partial consumption of the SWCNTs. The functionalization of the SWCNTs is highly specific with formation of carboxyl, hydroxyl and carbonyl groups. On the other hand this oxidation step is highly efficient for the oxidation of the catalytic impurities (Ni, Y) which can be easily removed by subsequent acid treatment. A final high temperature treatment indicates some incomplete restoration of the quality of the SWCNT surface.     

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.     

Growth of single-walled carbon nanotubes with controlled diameters and lengths by an aerosol method

On the basis of combined study of the transmission electron microscopy, scanning electron microscopy, Raman spectroscopy and ultraviolet–visible–near infrared absorption spectroscopy, the properties of the single-walled carbon nanotubes (SWCNTs), synthesized by aerosol (floating catalyst) chemical vapor deposition method by ferrocene vapor decomposition in the presence of carbon monoxide, are studied in details. The results show that increasing the temperature gives rise to the formation of high quality and large diameter SWCNTs. By monitoring the water-cooled probe position, both the bundle length and the diameter of the SWCNTs are effectively tuned due to the variation of the residence time and temperature profile in the reactor. An introduction of a small amount of CO₂ suppresses the growth of small diameter nanotubes and enlarges the mean diameter of SWCNT samples. The mean diameter of SWCNTs could be easily altered in a broad range from 1.1 to 1.9 nm during growth, which is essential for the SWCNT applications in optical and electronic devices.     

A simple and highly effective process for the purification of single-walled carbon nanotubes synthesized with arc-discharge

We developed a simple and highly effective process for the purification of single-walled carbon nanotubes (SWCNTs) synthesized with arc-discharge. The new process consists of two steps: (i) ultrasonic filtration of an aqueous acid solution of the SWCNTs, and (ii) heat-treatment at 430 °C for 1 h under a moisture-saturated N₂ atmosphere. This simple process results in the remarkably effective removal of impurities such as amorphous carbon, carbon nanoparticles, and metallic catalysts. Further, the whole purification process can be completed within 5 h, which is much faster than conventional acid purification processes, which require 50 h, and much less destructive than other conventional purification methods. In a gram-scale purification, the proposed purification method gave us 150 mg of purified SWCNTs with the purity of 96.2 wt% out of 1.0 g of as-prepared SWCNTs, which corresponds to ∼72% yield as for the initial composition of SWCNTs in the as-prepared soot. Field emission scanning electron microscopy, high resolution transmission electron microscopy, thermogravimetric analysis, X-ray diffractometry, and Raman spectroscopy were used to determine the effects of the new purification process on the SWCNTs.     

Synthesis of carbon nanocapsules and carbon nanotubes by an acetylene flame method

The fabrication of carbon nanocapsules and carbon nanotubes (CNTs) using an acetylene flame method was investigated. Carbon nanocapsules, a graphitic structure of nanoparticles with a hollow core, were synthesized using catalyst-free acetylene flames while CNTs were formed with the presence of cobalt-based catalysts in addition to acetylene flames. When the synthesis of these materials was carried out, the results showed that a massive amount of high-purity carbon nanocapsules with a particle size in the range of 15-30 nm can be produced with the acetylene flame method. The CNTs produced were multi-walled carbon nanotubes measuring a few micrometers in length and 20-30 nm in diameter. The acetylene flame method holds great potential for the cost-effective production of CNTs as well as carbon nanocapsules.     

Effectiveness of sorting single-walled carbon nanotubes by diameter using polyfluorene derivatives

Semiconducting single-walled carbon nanotubes (SWCNTs) sorted by conjugated polymers are of great interest for electronic and optoelectronic applications. Here we demonstrate by optical methods that the selectivity of conjugated polymers for semiconducting SWCNTs is influenced by the structure of their side-chains and/or the molecular weight of the macromolecules, and that side chain functionalities determine the solubility in different dispersion media. Moreover, high resolution time-resolved photoluminescence measurements provide evidence of energy transfer from tubes with larger band gaps compared to those with smaller band gaps coexisting in SWCNT bundles.     

Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes

A systematic study was carried out to dope single-walled carbon nanotube (SWNT) bundles with varying amounts of boron using the pulsed laser vaporization technique. Targets containing boron concentrations ranging from 0.5 to 10 at.% boron were prepared by mixing elemental boron with carbon paste and the Co/Ni catalysts. The laser-generated products that were obtained from these targets were characterized by high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), thermoelectric power (TEP) measurements, and Raman scattering experiments. Electron microscopy and Raman studies revealed that the presence of various levels of boron concentration in the target strongly affected the products that were prepared. SWNTs were found in the products prepared from targets containing up through 3 at.% boron, and high resolution EELS estimated that less than 0.05-0.1 at.% boron is present in the SWNT lattice. The absence of SWNT bundles in the products derived from targets containing more than 3 at.% boron implies that the presence of excess boron in the carbon plume severely inhibits the carbon nanotube growth. The overall effect of the boron incorporation primarily leads to: (i) a systematic increase in intensity of the disorder-induced band (D-band) upon boron doping, with increasing D-band intensity observed for higher doping levels, (ii) a systematic downshift in the G′-band frequency due the relatively weaker C-B bond, and (iii) a non-linear variation in the RBM and G′-band intensities which is attributed to shifts in resonance conditions in the doped tubes. Resonant Raman spectroscopy thus provides large changes in the intensity of prominent features even when the dopant concentration is below the detectable limit of EELS (0.05-0.1 at.%). Thermoelectric power data also provide complementary evidence for the presence of a small boron concentration in the SWNT lattice which transforms the SWNTs into a permanently p-type material.     

Continuous production of single-walled carbon nanotubes using a supported floating catalyst

Using catalytic decomposition, a technique for the production of singe-walled carbon nanotubes (SWCNTs) is reported with a production rate up to 6 g h⁻¹ after purification, and scaling capability up to 220 g h⁻¹. This is achieved by injection of pre-prepared alumina supported catalyst powder into a modified vertical floating reactor. The product is collected in several cyclones connected in series. Wide range Raman studies (laser excitations from λ = 1064 to 488 nm) and temperature programmed oxidation measurements of the samples collected from the different cyclones show that SWCNTs were separated in situ by tube diameter. This is attributed to the different residual times of the catalyst in the reaction zone depending on particle diameter. A series of computational fluid dynamics calculations of the flow and heat transfer in the reactor, as well as modeling of catalyst particle transport reveals the parametrical dependence of the process.     

Preparation of double-walled carbon nanotubes from fullerene waste soot by arc-discharge

Fullerene waste soot (FWS) was used as raw material to fabricate double-walled carbon nanotubes (DWCNTs) by arc-discharge in a mixture of Ar and H₂ (2:1, v/v) at 300 Torr. The results of transmission electron microscope and Raman spectroscopy indicate that the high quality FWS-derived DWCNTs can be synthesized by arc-discharge method.     

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.     

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.     

Bending single-walled carbon nanotubes into nanorings using a Pickering emulsion-based process

Single-walled carbon nanotube (SWCNT) nanorings have been fabricated on a large scale using a Pickering emulsion-based process. The formation mechanism was attributed to liquid/liquid interface-induced SWCNT bending. Mechanical analysis shows that curved water/1,2-dichlorobenzene interface created during the miniemulsion process is sufficient to bend the SWCNT into closed rings. Raman spectroscopy was used to study SWCNT structural change after the nanoring formation. It was shown that compressive and tensile strains were introduced in these rings. We anticipate that a variety of functionalized SWCNT nanorings can be fabricated using our method for various applications.     

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.