Modification of multi-walled carbon nanotubes for electric double-layer capacitors: Tube opening and surface functionalization

Multi-walled carbon nanotubes (MWCNTs) obtained opening the closed ends and using surface functionalization by means of a combination of partial oxidation in air and chemical modifications are characterized systematically in 0.3 M H₂SO₄ between 0 and 1.0 V, and these nanotubes were planned to be used as electrode materials in electric double-layer capacitors (EDLCs). Opening of MWCNTs, clearly observed by means of transmission electron microscopy (TEM), can be easily achieved by the partial oxidation in air through a seven-step temperature program identified by thermogravimetric/differential thermal analyses (TG/DTA). An increase in 175% specific capacitance is obtained for the MWCNTs, partially oxidized in air and chemically modified in H₂SO₄+HNO₃. The temperature-programmed desorption (TPD) data showed that evolutions of CO and CO₂ are, respectively, promoted by the application of partial oxidation in air and chemical modification in H₂SO₄+HNO₃. The above increase in specific capacitance for modified MWCNTs is attributed to an obvious increase in the BET surface area (double-layer capacitance) and the density of oxygen-containing surface functional groups (pseudocapacitance).     

Electronic properties of double-layer carbon nanotubes

The electronic spectra for double-wall zigzag and armchair nanotubes are found. The influence of nanotube curvatures on the electronic spectra is also calculated. Our finding that the outer shell is hole doped by the inner shell is in the difference between Fermi levels of individual shells which originate from the different hybridization of π orbital. The shift and rotation of the inner nanotube with respect to the outer nanotube are investigated. We found stable semimetal characteristics of the armchair DWNTs in regard of the shift and rotation of the inner nanotube. We predict the shift of k_F towards the bigger wave vectors with decreasing of the radius of the armchair nanotube.     

Transverse elasticity of multi-walled carbon nanotubes

A discrete shell model is proposed to describe the radial deformation of carbon nanotubes under a hydrostatic pressure and the radial Young's modulus of (single- or multi-walled) nanotubes is obtained. It is found that the radial modulus decreases with increasing tube diameter while increases with increasing number of layers. The computational results agree well with the previous results of SWNTs and indicate that the radial modulus of carbon nanotubes is independent of the Poisson's ratio.     

Q-switched ytterbium doped fiber laser using multi-walled carbon nanotubes saturable absorber

A Q-switched ytterbium-doped fiber laser(YDFL)is proposed and demonstrated using a newly developed multi-walled carbon nanotubes polyethylene oxide(MWCNTs-PEO)film as a passive saturable absorber(SA).The saturable absorber is prepared by mixing the MWCNTs homogeneous solution into a dilute PEO polymer solution before it is left to dry at room temperature to produce thin film.Then the film is sandwiched between two FC/PC fiber connectors and integrated into the laser cavity for Q-switching pulse generation.The laser generates a stable pulse operating at wavelength of 1060.2 nm with a threshold pump power of 53.43 mW.The YDFL generates a stable pulse train with repetition rates ranging from7.92 to 24.27 kHz by varying 980-nm pump power from 53.42 to 65.72 mW.At 59.55-mW pump power,the lowest pulse width and the highest pulse energy are obtained at 12.18μs and 143.5 nJ,respectively.     

Q-switched ytterbium doped carbon nanotubes fiber laser using multi-walled saturable absorber

A Q-switched ytterbium-doped fiber laser （YDFL） is proposed and demonstrated using a newly developed multi-walled carbon nanotubes polyethylene oxide （MWCNTs-PEO） film as a passive saturable absorber （SA）. The saturable absorber is prepared by mixing the MWCNTs homogeneous solution into a dilute PEO polymer solution before it is left to dry at room temperature to produce thin film. Then the film is sandwiched between two FC/PC fiber connectors and integrated into the laser cavity for Q-switching pulse generation. The laser generates a stable pulse operating at wavelength of 1060.2 nm with a threshold pump power of 53.43 mW. The YDFL generates a stable pulse train with repetition rates ranging from 7.92 to 24.27 kHz by varying 980-nm pump power from 53.42 to 65.72 mW. At 59.55-mW pump power, the lowest pulse width and the highest pulse energy are obtained at 12.18 μs and 143.5 n J, respectively.     

XPS study of fluorinated carbon multi-walled nanotubes

Arc-produced carbon multi-walled nanotubes (MWNTs) were fluorinated at 420 °C in a flow of diluted F₂ gas containing small admixture of HF gas. Fluorinated materials (F-MWNTs) with 10–55 wt.% fluorine content were studied by XPS. It was shown that fluorination begins at the external layers of nanotubes and the reaction front propagates inside the multi-layer particles in concert with structural deterioration of graphene layers. The C₂F stoichiometry still allows MWNT wall integrity, similar to known for SWNTs. The fluorine contents in the product can noticeably exceed this higher fluorine limit for tube stability. The position of the F 1s line at 688.2 eV does not depend on the fluorine concentration. Nearly covalent C–F bonds dominate the F-MWNT samples, with a small quantity (2–9%) of ionic bonds also present. Fluorinated carbon tends to spatially separate from non-fluorinated carbon.     

Nitrogen-doped multi-walled carbon nanotubes for paracetamol sensing

A novel sensor consisting of nitrogen-doped multi-walled carbon nanotubes was fabricated by means of chemical vapor deposition technique with decomposition of acetonitrile onto oxidized silicon wafer using ferrocene as catalyst. The electrochemical response of carbon nanotubes-based sensor towards oxidation of paracetamol to N-acetyl-p-quinone imine was investigated in phosphate buffer solution (pH 7.0) by means of standard electrochemical techniques. A quasi-reversible response for oxidation of paracetamol was identified on carbon nanotubes-based sensor with detection limit and sensitivity of 0.485 μM and 0.8406 A M^?1 cm^?2, respectively. It was found that the nitrogen doping in carbon nanotubes enhances the sensor's detection ability. Namely, electrochemical studies performed on film consisting of pristine carbon nanotubes reveal as well quasi-reversible response towards oxidation of paracetamol but nevertheless poorer detection ability and sensitivity (0.950 μM; 0.601 A M^?1 cm^?2). The findings strongly suggest the application of nitrogen-doped carbon nanotubes in biosensing.     

Guided waves characteristics of multi-walled carbon nanotubes

The theoretical analysis of propagation of guided waves in the multi-walled carbon nanotubes is presented within the framework of the classical electrodynamics. Electronic excitations of each wall of the system are modeled as an infinitesimally thin cylindrical layer of the π-electrons, whose dynamics are described by means of the fluid theory. General expressions of dispersion relations are obtained for the electromagnetic wave with the transverse magnetic and transverse electric modes, respectively, by solving Maxwell and fluid equations with appropriate boundary conditions.     

多壁碳纳米管光限幅特性的研究

用化学气相沉积法制备了多壁碳纳米管,并将其溶解在甲苯溶液中.用波长为1064nm的皮秒脉冲激光测量该样品的透过率,发现了非常明显的光限幅特性.当入射光强较小时,透射光强度随入射光强度的增大而增大,输出与输入为线性关系;随着入射光强的增大,透射光强增长的速度明显变慢,并逐渐趋于饱和.当入射光强度较小时,样品的透过率接近100%;而当入射光强为8GW/cm²时,非线性透过率达到30%.根据三光子吸收理论计算,理论拟合与实验结果非常符合,说明多壁碳纳米管的三光子吸收产生了光限幅效应.实验测 关键词： 多壁碳纳米管 光限幅 三光子吸收     

Optimization of field emission properties from multi-walled carbon nanotubes using ceramic fillers

The field emission properties of multi-walled carbon nanotubes were examined using a screen-printed thick film with a diode-type configuration in a vacuum. The effects of various concentrations of two different ceramic fillers, indium tin oxide (ITO) powder and a glass frit, on the emission current density and turn-on field were evaluated. The emission properties of both pastes were dependent on the amount of filler. Considerably enhanced emission properties were obtained with the paste containing 5–10 wt.% of either ITO or the glass frit compared with those without a filler. The paste containing the ceramic filler showed enhanced emission properties compared with that containing the 5 wt.% Ag conventionally used, which confirmed the importance of the filler. The paste containing 10 wt.% ITO represented an emission current density of 176.4 μA/cm² at 5 V/μA, a turn-on field of 1.87 V/μA for an emission current density of 1 μA/cm² and a field enhancement factor of 7580. The paste formulation was also found to be suitable for fine patterning using UV-lithography techniques. A long-term stability test for 110 h of a paste containing 10 wt.% ITO revealed a half-life of approximately 30000 h, which is appropriate for commercial applications.     

Low voltage STEM imaging of multi-walled carbon nanotubes

We present high magnification STEM images of multi-walled carbon nanotubes recorded with a 5 keV electron beam using a Helios Dual Beam microscope and a dedicated multi-segment transmission (STEM) detector. Images of carbon nanotubes recorded with bright-field (BF), annular dark-field (ADF) and high angle annular dark-field (HAADF) signals all show high contrast features, with internal structures 1-2 nm in width clearly revealed in the STEM images. Thicker regions of the nanotubes appear to show an unusual contrast reversal when comparing ADF and HAADF images. An understanding of the image contrast, and its dependence on thickness, is obtained by computing simulations of the ADF and HAADF images using Monte-Carlo software taking into account electron scattering in the nanotube.     

Dispersion of multi-walled carbon nanotubes in biocompatible dispersants

Owing to their phenomenal electrical and mechanical properties, carbon nanotubes (CNT) have been an area of intense research since their discovery in 1991. Different applications for these nanoparticles have been proposed, among others, in electronics and optics but also in the medical field. In parallel, emerging studies have suggested potential toxic effects of CNT while others did not, generating some conflicting outcomes. These discrepancies could be, in part, due to different suspension approaches used and to the agglomeration state of CNT in solution. In this study, we described a standardized protocol to obtain stable CNT suspensions, using two biocompatible dispersants (Pluronic F108 and hydroxypropylcellulose) and to estimate the concentration of CNT in solution. CNT appear to be greatly individualized in these two dispersants with no detection of remaining bundles or agglomerates after sonication and centrifugation. Moreover, CNT remained perfectly dispersed when added to culture medium used for in vitro cell experiments. We also showed that Pluronic F108 is a better dispersant than hydroxypropylcellulose. In conclusion, we have developed a standardized protocol using biocompatible surfactants to obtain reproducible and stable multi-walled carbon nanotubes suspensions which can be used for in vitro or in vivo toxicological studies.     

Covalent functionalization of multi-walled carbon nanotubes by lipase

Lipase from Candida rugosa was covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a self-catalytic mechanism. A variety of characterization techniques including FTIR, Raman spectroscopy, and XPS were employed to demonstrate the formation of the ester linkage between lipase and MWNTs. The MWNTs-lipase biocomposites showed significantly increased solubility in some common-used organic solvents, such as THF, DMF and chloroform. This study may offer a novel and facile route for covalent modification of carbon nanotubes, and expand the potential utilization of both lipases and MWNTs in the fields of biocatalyst and biosensor.     

Field electron emission images of multi-walled carbon nanotubes

Field electron emission microscope images from multi-walled carbon nanotubes can typically be characterized by the presence of five pentagons surrounding a sixth central pentagon. The observations of bright line centered interference patterns between adjacent pentagons in the field electron emission microscope images of multi-walled carbon nanotubes have been reported in the literature. We have observed a shift from bright to dark line centered interference patterns and associated this with the presence of surface adsorption. In order to identify the origin of the contaminant, multi-walled carbon nanotubes were dosed with H₂, H₂O, CO and O₂ and then imaged in the field electron emission microscope. Only the samples exposed to O₂ showed a shift from a bright line centered pattern between adjacent pentagons of a clean surface to a dark line centered pattern when one pentagon was contaminated or a bright line centered pattern when both adjacent pentagons become contaminated. The results of the experimental studies and the modeling of the changes in the field emission pattern as phase shifts in the wave function of the tunneling electrons due to modifications in the surface work function are presented.     

Preparation and characterization of amphiphilic multi-walled carbon nanotubes

Multiwalled carbon nanotubes (MWCNTs, average diameter 8 nm) functionalized by N-vinyl pyrrolidone (NVP) were synthesized by radical polymerization and characterized by Fourier transform infrared and Raman spectroscopies, thermogravimetric analysis and transmission electron microscopy. These NVP–MWCNTs exhibit remarkable solubility in water, ethanol and dimethyl formamide. The polyvinyl pyrrolidone can be attached onto the surface of the MWCNTs and the degree of functionalization is affected by NVP content. The functionalization causes possible grafting reaction and solid physical coating between MWCNTs and PVP.     

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.     

Radial buckling of multi-walled carbon nanotubes under hydrostatic pressure

Radial buckling stresses of carbon nanotubes (CNTs) need to be studied in high-pressure resonance Raman scattering spectrum. In this work, the closed-form expression of the critical buckling stress of multi-walled carbon nanotubes (MWCNTs) under hydrostatic pressure is derived that can be conveniently employed. Using the derived formulae, the critical buckling stresses of single-walled carbon nanotubes and double-walled carbon nanotubes with different diameters are calculated. The results are in good agreement with other reported literatures. In addition, the critical buckling stresses of each layer of a quintuple-walled CNT in different buckling modes are predicted, showing that the buckling instability can occur not only in the outermost rolled layer, but also in other rolled layer of MWCNTs by considering different diameters and buckling modes.     

Temperature enhanced growth of ultralong multi-walled carbon nanotubes forest

This work demonstrates a method to synthesize ultralong multi-walled carbon nanotubes (MW-CNTs) forest with high growth rate using the three-zone temperature chemical vapor deposition (TZT-CVD). The effect of temperature difference in the TZT-CVD is to sustain the lifetime of the catalyst and hence increase the growth efficiency. By optimizing the growth variables, TZT-CVD produced MW-CNTs forest with a height up to 4.27 mm in 60 min. The CNT synthesis ratio, an ultimate figure of merit is 712 times and the carbon source consumption is 4% compared to that of single-zone temperature CVD.     

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.