Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Effect of Thermal Treatment on the Structure of Multi-walled Carbon Nanotubes

The effects of vacuum annealing and oxidation in air on the structure of multi-walled carbon nanotubes (MWCNTs) produced by a large-scale catalytic chemical vapor deposition (CCVD) process are studied using Raman spectroscopy and transmission electron microscopy (TEM). A detailed Raman spectroscopic study of as-produced nanotubes has also been conducted. While oxidation in air up to 400°C removes disordered carbon, defects in tube walls are produced at higher temperatures. TEM reveals that MWCNTs annealed at 1,800°C and above become more ordered than as-received tubes, while the tubes annealed at 2,000°C exhibit polygonalization, mass transfer and over growth. The change in structure is observable by the separation of the Raman G and D′ peaks, a lower R-value (I _D/I _G ratio), and an increase in the intensity of the second order peaks. Using wavelengths from the deep ultraviolet (UV) range (5.08 eV) extending into the visible near infrared (IR) (1.59 eV), the Raman spectra of MWCNTs reveal a dependence of the D-band position proportional to the excitation energy of the incident laser energies.     

Effects of gas composition on the growth of multi-walled carbon nanotube

This paper studies the effects of different gas compositions on the growth of multi-walled carbon nanotube (MWCNT) films by using an electron cyclotron resonance chemical vapor deposition (ECR-CVD) method. The Raman spectrum was employed to explore the composition of the MWCNT films grown under different mixtures of C₃H₈ and H₂. The results showed that the optimum relative intensity ratio of the D band to G band (i.e., I_D/I_G) is 2 for the cases considered in this study. In addition, the morphology and microstructure of the MWCNTs were examined by field emission scanning electron microscopy (FE-SEM) and field emission gun transmission electron microscopy (FEG-TEM). Furthermore, atomic force microscopy (AFM) and scanning thermal microscopy (SThM) were used to study the surface topography and thermal properties of the MWCNTs.     

Origin of the low-frequency band in Raman spectra of multi-walled carbon nanotubes synthesized by the CVD method

The origin of the low-frequency band (250–300 cm^?1) in the Raman spectra of multi-walled carbon nanotubes (MWCNTs) produced by the CVD method has been studied. The studies performed by Raman spectroscopy, transmission electron microscopy, Auger spectroscopy, and X-ray photoelectron spectroscopy after chemical and thermal treatments allow the assumption that this band belongs to radial vibrations of carbon atoms in internal walls of MWCNTs.     

Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of SWNTs produced by a XeCl excimer laser ablation at high temperatures

Synthesis of single-wall carbon nanotubes (SWNTs) was carried out by an ablation method using a XeCl excimer laser. It was irradiated onto a graphite target containing Co and Ni at the temperatures of 1073, 1173, 1273, 1373, 1473, 1523 and 1623 K under the atmosphere (0.1 MPa) of Ar gas with the flow rate of 12 ml/min. The measurement by a scanning/transmission electron microscope and Raman spectroscopy found the formation of SWNTs with the diameter of about 1.3 nm and the length of about 2 μm in ablated carbonaceous soot. The ratio of peak intensity of 1590 cm⁻¹ (G band) to that of 1335 cm⁻¹ (D band) in the high frequency Raman spectra increased with increasing the ambient temperature. The radial breathing mode (RBM) in the low frequency Raman spectra shows that the mean diameter of SWNTs increased with increasing the ambient temperature.     

Nanotitania-coated multi-walled carbon nanotube composite by facile colloidal processing route for photocatalytic applications

Multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanocomposites (MWCNTs/TiO₂) were fabricated by a simple novel colloidal processing route and tested as a photocatalyst for degradation of methylene blue under UV irradiation. The novel idea behind this work is to make MWCNTs and TiO₂ nanoparticle suspensions separately highly oppositely charged and utilize the electrostatic force of attraction between two entities to deposit nanotitania onto MWCNTs surface. Particle charge detector, scanning electron microscopy, transmission electron microscope, energy dispersive X-rays, X-rays diffraction (XRD), and Raman spectroscopy were used to characterize the composite. XRD and Raman spectroscopic analysis showed the crystalline structure of deposited TiO₂ over MWCNTs surface structure as anatase phase. It was found that MWCNTs/TiO₂ composite structure have much higher photocatalytic activity compared to TiO₂ nanoparticles. The composite material developed may find potential applications in the degradation of organic pollutants in aqueous medium under UV irradiation.     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

Optimization of cuprous oxide nanocrystals deposition on multiwalled carbon nanotubes

Cu (I) phenyl acetylide was used as a source of copper to achieve a homogeneous distribution of Cu₂O nanocrystals (10–80 nm) decorated on multiwalled carbon nanotubes (MWCNTs) having an average diameter of 10 nm. Pristine MWCNTs were first oxygen-functionalized by treating them with a mixture of concentrated (H₂SO₄/HNO₃ : 3/1) acids and the products were characterized by X-ray powder diffraction, transmission and scanning electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and thermogravimetric analysis. An easy, efficient and one-step impregnation method was followed to produce copper-containing nanoparticles on the MWCNTs. The copper-treated MWCNTs dried at room temperature were seen to be well decorated by copper-containing nanoparticles on their outer surface. The MWCNTs were then heat-treated at 400 °C in a nitrogen atmosphere to produce a homogeneous distribution of cuprous oxide nanocrystals on their surface. By varying the ratio of copper to oxygen-functionalized MWCNTs, Cu₂O nanocrystals decorated on MWCNTs with different copper content can be obtained.     

聚(2,5-二丁氧基)对苯乙炔/多壁碳纳米管复合材料的制备和性能研究

通过原位聚合法制备了聚（2,5-二丁氧基）对苯乙炔/多壁碳纳米管（PDBOPV/MWCNTs）复合材料.红外光谱和拉曼光谱证实了在MWCNTs表面的包覆层为PDBOPV.高分辨透射电子显微镜观察发现,PDBOPV/MWCNTs复合材料直径为35—45 nm,其中PDBOPV包覆层厚度约为15 nm.紫外—可见吸收光谱表明随着MWCNTs含量的增加,PDBOPV/MWCNTs的吸收发生红移且强度提高.荧光光谱研究表明随着MWCNTs含量的增加,PDBOPV/MWCNTs的最大发射波长发生蓝移且强度减小,MWCNTs与PDBOPV之间形成了光致电子转移体系,使得π电子离域程度增加,并且导致荧光量子效率降低.根据E_g与入射光子能量hν的关系,拟合了PDBOPV/MWCNTs薄膜的光学禁带宽度,发现随着MWCNTs的增加,E_g逐步减小.采用简并四波混频方法测试它们的三阶非线性极化率χ^（3）,结果发现随着MWCNTs含量的增加,PDBOPV/MWCNTs复合体的非线性光学响应逐渐增强,这说明PDBOPV与MWCNTs之间形成了分子间光致电子转移体系,产生了复杂的分子间π-π电子非线性运动. 关键词： 聚（2 5-二丁氧基）对苯乙炔 多壁碳纳米管 复合材料 光致发光     

How does the substrate affect the Raman and excited state spectra of a carbon nanotube?

We study the optical properties of a single, semiconducting single-walled carbon nanotube (CNT) that is partially suspended across a trench and partially supported by a SiO₂-substrate. By tuning the laser excitation energy across the E ₃₃ excitonic resonance of the suspended CNT segment, the scattering intensities of the principal Raman transitions, the radial breathing mode (RBM), the D mode and the G mode show strong resonance enhancement of up to three orders of magnitude. In the supported part of the CNT, despite a loss of Raman scattering intensity of up to two orders of magnitude, we recover the E ₃₃ excitonic resonance suffering a substrate-induced red shift of 50 meV. The peak intensity ratio between G band and D band is highly sensitive to the presence of the substrate and varies by one order of magnitude, demonstrating the much higher defect density in the supported CNT segments. By comparing the E ₃₃ resonance spectra measured by Raman excitation spectroscopy and photoluminescence (PL) excitation spectroscopy in the suspended CNT segment, we observe that the peak energy in the PL excitation spectrum is red-shifted by 40 meV. This shift is associated with the energy difference between the localized exciton dominating the PL excitation spectrum and the free exciton giving rise to the Raman excitation spectrum. High-resolution Raman spectra reveal substrate-induced symmetry breaking, as evidenced by the appearance of additional peaks in the strongly broadened Raman G band. Laser-induced line shifts of RBM and G band measured on the suspended CNT segment are both linear as a function of the laser excitation power. Stokes/anti-Stokes measurements, however, reveal an increase of the G phonon population while the RBM phonon population is rather independent of the laser excitation power.     

Nanoporous AlN particles production from a solid-state metathesis reaction

This paper reports that nanoporous AlN particles are synthesized from solid-state metathesis reactions using AlCl₃ and Mg₃N₂ as reactants. The samples are characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, high-resolution transmission electron microscopy (HRTEM), ultraviolet--visible (UV--vis) absorption spectroscopy and Raman spectroscopy. The results show that samples with walls 10 nm in thickness and pores between 10 nm and 100 nm in diameter were produced successfully from these reactions, and their band gap and vibration modes agree with those of AlN bulk crystal.     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.     

Detection of pathogenic microorganisms using biosensor based on multi-walled carbon nanotubes dispersed in DNA solution

The present paper introduces a facile and cost-effective route for the direct dispersion of multi-walled carbon nanotubes (MWCNTs) in DNA solution. Their application in detecting Escherichia coli O157:H7 using DNA biosensor was demonstrated. The dispersion state of the MWCNTs was characterized via UV–Vis spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy. The interaction between DNA sequence and the MWCNTs was investigated using Raman spectroscopy and Fourier transform infrared spectroscopy. As-obtained MWCNT solution was used in the preparation of DNA sensor. Results revealed that the developed DNA sensor can detect a DNA target as low as 1 nM in a buffer solution. The sensitivity of the DNA sensor reached approximately 0.19 nM/mV. The effect of dispersion parameters, including pH values, DNA concentration, ion strength, and sonication time, on sensor response was also studied. The DNA sensor can respond well to 120 min of sonication time, a pH value of 9, and 20 μM of DNA sequence concentration. The results of the present study showed a potential application of the DNA sensor in the detection of Escherichia coli O157:H7.     

超长定向含铁多壁碳纳米管阵列的制备

采用无模板化学气相沉积法,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置制备了定向碳纳米管阵列。运用扫描电子显微镜、透射电子显微镜、拉曼光谱和X射线衍射仪等对定向碳纳米管阵列的形貌、成分和物相进行细致的分析和表征。结果表明:制得的碳纳米管阵列具有良好的定向性和多壁管状结构,并且石墨化程度高;碳纳米管中除碳元素外,管中包含有少量以纳米颗粒和纳米线形式存在的铁及其化合物,主要成分是铁和碳化铁。结合碳纳米管的制备和透射电子显微镜分析表征结果,认为超长碳纳米管阵列的生长模式为底部生长方式,即经历催化剂分解、催化、成核、长大、中毒、凝聚成粒和连接成线的循环过程,正是由于碳源和催化剂的连续供应促成了碳纳米管阵列的快速定向生长。     

Phonon confinement in individual titanium dioxide nanowires

Size effects on the phonon modes have been unambiguously observed on single individual titanium dioxide (TiO₂) nanowire using Raman spectroscopy. A template-free oxidation process using ethanol vapor was developed to control the growth and the density, length, and size distribution of the TiO₂ nanowires. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the morphology, crystalline phases and microstructures. Using a confocal laser probe, Raman spectroscopy revealed in the individual rutile TiO₂ nanowire, the E_g, A_1g vibration modes which are confined in the radial directions. Along the single-crystalline nanowire axis, the systematic size-dependent variations in the center-shift, broadening as well as the shape asymmetry of the Raman peaks can be well explained in terms of the phonon confinement model.     

Evolution of Co n Al clusters and chemisorption of hydrogen on Co n Al clusters

Multiwall carbon nanotubes (MWCNTs, 1?C3???M in length and 20?C25?nm in diameter) were initially functionalized with a 2,2??:6??2??-terpyridine-chelated ruthenium(II) complex by covalent amidation. The resulting functionalized ruthenium MWCNTs (RuMWCNTs, 1?C2???M in length and 10?C20?nm in diameter) were characterized by thermogravimetric analysis, X-ray photoelectronic spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM). Thermogravimetric experiments of RuMWCNTs show that the functional group coverage of terpyridine?Crutheniun?Cterpyridine (tpy?CRu?Ctpy) is 0.7036?mmol/1.0?g carbon. The XPS results show N1s and Ru3d^5/5 signals, confirming the presence of tpy?CRu?Ctpy groups on the surface of MWCNTs. The FTIR spectra of the RuMWCNTs display the typical stretching mode of the carboxyl group (amide I) and a combination of amide N?CH and C?CN stretching mode (amide II). The Raman D- and G-line peak intensity ratio of RuMWCNTs (ID/IG 2.21) exceeds that of pristine MWCNTs (ID/IG 1.93), suggesting covalent bonding of tpy?CRu?Ctpy to MWCNTs and supporting the disruption of the graphitic integrity due to the proposed covalent functionalization. High-resolution SEM images confirm that tpy?CRu?Ctpy moieties are interconnected or attached as aggregated structures (100?C200-nm range) on the surfaces of the carbon nanotubes after functionalization. The electrical property of RuMWCNTs depicts higher resistance (10.10?M???) than that of OX-MWCNTs (15.38?k??).     

Hydrostatic pressure effects on oxygen-related irradiation-produced defects in silicon

Abstract

Hydrostatic pressure has been used as a variable to investigate the E_c-0.164 eV acceptor level for the oxygen-vacancy (O—V) defect in γ-ray irradiated Si, and the annealing/formation of oxygen-related defects in neutron-irradiated Si. The acceptor level is found by deep level transient spectroscopy to move closer to the conduction band and away from the valence band at rates of 3.9 meV/kbar and 2.4 meV/kbar, respectively, i.e., the level moves higher in the gap. There is also a relatively large inward (outward) breathing mode lattice relaxation (4.6±1.2 ų/electron) accompanying electron emission (capture) from this level. Both results reflect the antibonding nature of the level and are qualitatively consistent with the Watkins—Corbett model for the O—V defect. The annealing rate was found by infrared absorption to increase with pressure for the O—V defect at 350°C with a derived activation volume of ?4.5 ų/defect, where the negative sign implies inward relaxation (contraction) on annealing. Pressure has relatively little effect on annealing of the C—Si—O C(3) defect which is interstitial in nature, but strongly favors the formation of the dioxygen (2 oxygen atoms per vacancy, i.e., O₂—V) defect. The intensity of the O₂—V band after annealing at 20 kbar is 5 times higher than that following similar annealing at 0 kbar. Additionally, this intensity at 20 kbar is higher than that achievable by any isochronal or isothermal annealing steps at 0 kbar. These annealing/formation results are discussed qualitatively in terms of models for the various defects.     

Effect of different microwave-based treatments on multi-walled carbon nanotubes

Three new methods for the functionalization of multi-walled carbon nanotubes (MWCNTs) are reported using microwave (MW) energy and water as a mild chemical agent. In the first method we reported the effect of MW irradiation on a dispersion of MWCNTs in deionized water, in the second method we studied the exposing of MWCNT to microwave irradiation in the presence of steam, and in the third method we used microwave oven-generated plasma for the functionalization of MWCNTs. We also performed thermal oxidation and acid treatment as two conventional methods for oxidative functionalization of carbon nanotubes, to compare their effect with our results. Transmission electron microscopy (TEM) and Raman spectroscopy results showed that although these microwave methods introduced some defects to the carbon nanotubes, the damage was less severe than conventional treatments. X-ray photoelectron spectroscopy (XPS) measurements confirmed that the functionalization of carbon nanotubes by these methods favored hydroxyl groups, which are useful when further functionalization is required.