Origin of the 2450 cm Raman bands in HOPG, single-wall and double-wall carbon nanotubes

The second order Raman signals around the G′-band region of graphite and carbon nanotubes have been investigated at more than 15 excitation laser lines. Two distinct Raman bands have been observed around 2700 cm⁻¹; a prominent one is due to the so-called G′-band and the other is a weak band around 2450 cm⁻¹. Both two bands can be from the double resonance process involving two phonons around the K-point in the phonon dispersion of a two-dimensional graphite. The 2450 cm⁻¹-band has exhibited little power dependence, whereas the intensity of G′-band has shown large photon energy dependence as already reported. The 2450 cm⁻¹-band and the G′-band correspond to non-dispersive q = 0 and fully-dispersive q = 2k, respectively. From the phonon dispersion and the corresponding phonon frequency, the 2450 cm⁻¹-band can be assigned as an overtone mode of LO phonon (i.e. 2LO). This is revealed by calculated Raman spectra of graphite with proper electron-phonon matrix elements. The present study is the first report on the origin and assignment of the 2450 cm⁻¹-band, which is based on the double resonance Raman scattering.     

Charge transfer effects in acid treated single-wall carbon nanotubes

Single-wall carbon nanotubes (SWNTs) prepared by the arc discharge method were oxidized using nitric acid. The samples were analyzed by using Raman scattering and Fourier transformed infrared spectroscopy (FTIR). The FTIR results indicate the presence of -COOH acid groups in the treated samples. The up shifts observed in the radial breathing mode frequencies suggest that SWNTs behave as donors after the acid treatment, with charge transfer occurring from the nanotubes to the -COOH groups. Ab initio calculations of SWNTs interacting with -COOH acid groups support the charge transfer process from the nanotubes to the carboxyl groups.     

Synthesis of single-wall carbon nanotubes and long nanotube ribbons with Ho/Ni as catalyst by arc discharge

The effect of a new bimetallic catalyst Ho/Ni for synthesis of single-walled carbon nanotubes (SWNTs) by arc discharge has been studied. Long ribbons consisting of roughly-aligned SWNT bundles were obtained by a modified arc discharge apparatus. Ribbon lengths can reach as much as 20 cm. Both elements Ho and Ni play important roles in the synthesis of SWNTs with high yield and purity. Changes in the Ho and Ni concentration in the catalyst hardly affect the diameter distribution of SWNTs, but the yield and purity of SWNTs are very sensitive to the concentration. An optimal range of Ho/Ni compositions for synthesis of SWNTs with relatively high purity and yield is given.     

Synthesis and characterization of double-walled carbon nanotubes from multi-walled carbon nanotubes by hydrogen-arc discharge

Double-walled carbon nanotubes (DWNTs) were synthesized in a large scale by a hydrogen arc discharge method using graphite powders or multi-walled carbon nanotubes/carbon nanofibers (MWNTs/CNFs) as carbon feedstock. The yield of DWNTs reached about 4 g/h. We found that the DWNT product synthesized from MWNTs/CNFs has higher purity than that from graphite powders. The results from high-resolution transmission electron microscopy observations revealed that more than 80% of the carbon nanotubes were DWNTs and the rest were single-walled carbon nanotubes (SWNTs), and their outer and inner diameters ranged from 1.75 to 4.87 nm and 1.06 to 3.93 nm, respectively. It was observed that the ends of the isolated DWNTs were uncapped and it was also found that cobalt as the dominant composition of the catalyst played a vital role in the growth of DWNTs by this method. In addition, the pore structures of the DWNTs obtained were investigated by cryogenic nitrogen adsorption measurements.     

Biomolecules as selective dispersants for carbon nanotubes

Both single-wall or multi-wall nanotube growth result in a soot-like material that contains the desired product. The selective recovery of the nanotube product from this soot still represents a challenge. Methods to date either result in chemical modification of the nanotubes themselves, are time consuming or use expensive to produce polymers. Using a variety of biomolecules, we have been able to selectively suspend multi-wall carbon nanotubes in aqueous solutions while leaving behind the extraneous by-products in the precipitate. At comparable biomolecule to soot ratios, all biomolecules selectively retained more nanotubes than an organic polymer previously used to purify multi-wall nanotubes (PmPV—poly m-phenylene-co-2,5-dioctoxy-p-phenylenevinylene). The highest recovery as determined by Electron Paramagnetic Resonance was 56% of the available nanotubes. The method provides a simple, one-step, non-destructive purification process that facilitates the formation of pure multi-wall carbon nanotube containing biodispersions.     

Reduction of solubilized multi-walled carbon nanotubes

In this paper, the chemical reduction of solubilized multi-walled carbon nanotubes by LiAlH₄ was investigated. The amide groups on the nanotubes could be reduced to hydroxyl groups, which was confirmed by FTIR and XPS studies. The Raman spectroscopic investigation showed that the morphology of the nanotubes did not change after the reduction.     

多壁碳纳米管的拉曼光谱研究

显微拉曼光谱技术在微尺度测量方面具备无损、无接触和空间分辨率高的优势。实验考察了拉曼激光参数对多壁碳纳米管拉曼特征光谱的影响;确定了使用785 nm拉曼激发光波长来表征多壁碳纳米管及其复合材料,能够有效避免荧光效应;选择<5%的激光功率,能够有效避免热效应。     

Purification of multi-walled carbon nanotubes through microwave heating of nitric acid in a closed vessel

We demonstrate that microwave-assisted heating in 5 mL of nitric acid eliminates impurities, such as amorphous carbon, carbon nanoparticles, and metals, from multi-walled carbon nanotubes (MWNTs). Heating the closed reaction vessel under microwave irradiation at 160 °C for 30 min is a very effective means of purifying the MWNTs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images confirm that these reaction conditions are beneficial for removing the impurities and ensuring that the MWNTs remain intact. In contrast, a purification temperature of 180 °C provides too strongly oxidizing conditions that destroy the MWNTs. The ratio of the G and D bands in the Raman spectra also confirms that a temperature of 160 °C is optimal. The defect peak that we observed in the differential thermogravimetry (DTG) analysis of the raw material was not present after microwave purification. The presence of metal impurities in the MWNTs can be reduced significantly when using this method.     

A comparison between Raman spectroscopy and surface characterizations of multiwall carbon nanotubes

The distribution of graphene units with an axial symmetry gives rise to different types of carbon filaments: nanotubes, nanofilaments and classical fibers. In this work the surfaces of different multiwalled nanotubes are characterized by two complementary techniques: chemical ones based on Total Surface Area and Active Surface Area measurements, associated with a physical approach the Raman scattering spectroscopy. From analysis of Raman data we deduce the values of the in-plane coherence lengths, identified as L₁ the planar projection of graphene sheets, and we propose an analysis for the observed line-width behavior related to the graphitization step. From the surface chemical properties we establish a general relationship between the density of functional surface groups and the in plane coherence length L₁ for all types of MWNT. This analysis allows us to show the influence of both, the structural organization and the different treatments on the interfacial characteristics of these nanocarbons.     

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.     

Optimisation of the arc-discharge production of multi-walled carbon nanotubes

The effect of varying current density and pressure during arc generation on the yield and purity of multi-walled nanotube-containing carbon soot has been studied in this work. Various soots were produced and characterised qualitatively using transmission electron microscopy and quantitatively using electron paramagnetic resonance and thermogravimetric analysis. It was found that both yield and purity increase as current density and pressure are increased to the limit of our experimental investigations, i.e. 195 A/cm² and 500 Torr of helium. Under these conditions a yield of 24 mg/min soot containing 48% by mass nanotubes was obtained.     

Highly dispersed multi-walled carbon nanotubes in ethanol using potassium doping

We demonstrated the production of an effective dispersion of multi-walled carbon nanotubes (MWCNTs) in ethanol using potassium doping (π-stacking interaction). The homogeneous dispersion of individual MWCNTs was achieved without any contamination or severe disruption at the end caps or periphery of the tubes. Potassium as a doping material, phenanthrene as a nonpolar molecule, and 1,2-dimethoxyethane as a dipole solvent were used for our experiment. From UV-visible spectroscopy and visual observation, it was found that the dispersibility of the MWCNTs in ethanol was about 14 mg/dm³. High resolution transmission electron microscopy and Raman spectroscopy showed that disruption of the end caps of the tubes and severance along the tube axis were rarely found. The scanning electron microscopy and corresponding EDX results indicated that the key to the dispersion mechanism was the potassium doping, which is driven by π-stacking complex formation. We suggest that the dispersion of the MWCNTs was influenced by the potassium doping, which caused the enlargement and separation of the entangled-MWCNT networks, and was not affected by defects or modification of the surface morphology.     

Short carbon nanotubes produced by cryogenic crushing

A cryogenic crushing method to produce short carbon nanotubes (CNTs) is described. Crushing CNTs at liquid nitrogen temperature allows them to be shortened and make them appreciably soluble in a solvent without any dispersant. Typical lengths of less than 500 nm were obtained from 30 min crushing. The CNTs were characterized using atomic force microscopy, thermogravimetric, and Raman analyses.