On the mechanism of carbon nanotube formation: the role of the catalyst

This work examines the recent developments in non-traditional catalyst-assisted chemical vapour deposition of carbon nanotubes (CNTs) with a view to determining the essential role of the catalyst in nanotube growth. A brief overview of the techniques reliant on the structural reorganization of carbon to form CNTs is provided. Additionally, CNT synthesis methods based upon ceramic, noble metal, and semiconducting nanoparticle catalysts are presented. Experimental evidence is provided for CNT growth using noble metal and semiconducting nanoparticle catalysts. A model for CNT growth consistent with the experimental results is proposed, in which the structural reorganization of carbon to form CNTs is paramount.     

On the mechanism of carbon nanotube formation: I. The thermodynamics of formation of carbon molten drops in a metallic catalyst

Carbon molten drops in a metallic catalyst are known to be nucleation centers for carbon nanotubes. The problem of the kinetics of condensation of such drops in wide concentration ranges of carbon and metal vapors is considered. The equilibrium distribution of the drops over the size and mole fraction of the components is obtained. The main result is the calculation of the quasi-steady-state rate of condensation of the molten drops in a supersaturated carbon vapor. This result forms the basis for the calculation of the characteristics of explosive and rapid condensation of the vapor upon its cooling. This calculation is performed in the next part of this work.     

On the mechanism of carbon nanotube formation: II. The kinetics of explosive condensation of carbon molten drops in a metallic catalyst

The preliminary stage of the formation of carbon nanotubes by the vapor-liquid-drop mechanism is considered as applied to the condensation of drops from carbon and metal vapors. The problem of the condensation of molten drops is solved for a wide concentration range for both vapors at a condensation temperature. It is shown that, at very high concentrations of the metal vapor (10¹⁸–10¹⁹ cm⁻³) and high temperatures (about 0.3 eV), peculiar heterogeneous condensation of the drops can occur at huge supersaturation of the carbon vapor and the saturated metal vapor. This problem of the condensation of the binary vapor is of methodical interest. This condensation is shown to be unrealizable in real experiment at the parameters of the carbon and metal vapors; it virtually merges with the homogeneous condensation of the metal vapor. The maximum concentration of the carbon vapor below which carbon condenses into drops and above which carbon condenses into amorphous soot particles is calculated. The calculation makes it possible to propose a new approach to the controlled growth of carbon nanotubes.     

Economic assessment of single-walled carbon nanotube processes

The carbon nanotube market is steadily growing and projected to reach $1.9 billion by 2010. This study examines the economics of manufacturing single-walled carbon nanotubes (SWNT) using process-based cost models developed for arc, CVD, and HiPco processes. Using assumed input parameters, manufacturing costs are calculated for 1 g SWNT for arc, CVD, and HiPco, totaling $1.9 billion by 2010. This study examines the economics of manufacturing single-walled carbon nanotubes (SWNT) using process-based cost models developed for arc, CVD, and HiPco processes. Using assumed input parameters, manufacturing costs are calculated for 1 g SWNT for arc, CVD, and HiPco, totaling 1,906, 1,706, and1,706, and 485, respectively. For each SWNT process, the synthesis and filtration steps showed the highest costs, with direct labor as a primary cost driver. Reductions in production costs are calculated for increased working hours per day and for increased synthesis reaction yield (SRY) in each process. The process-based cost models offer a means for exploring opportunities for cost reductions, and provide a structured system for comparisons among alternative SWNT manufacturing processes. Further, the models can be used to comprehensively evaluate additional scenarios on the economics of environmental, health, and safety best manufacturing practices.     

Microscopic formation mechanism of nanotube peapods

Using molecular dynamics calculations, we investigate the absorption of a C(60) molecule in a (10,10) nanotube either through the open end or a large defect in the tube wall as possible scenarios for the hierarchical self-assembly of (C(60))(n)@(10,10) "nano-peapods." We find the absorption through a defect to be significantly more efficient than the end-on absorption. This process occurs most likely within a narrow launch velocity range for the fullerene that agrees well with the observed optimum temperature window for peapod formation.     

Pattern formation on carbon nanotube surfaces

Calculations of fluorine binding and migration on carbon nanotube surfaces show that fluorine forms varying surface superlattices at increasing temperatures. The ordering transition is controlled by the surface migration barrier for fluorine atoms to pass through next neighbor sites on the nanotube, explaining the transition from semi-ionic low coverage to covalent high coverage fluorination observed experimentally for gas phase fluorination between 200 and 250 degrees C. The effect of solvents on fluorine binding and surface diffusion is explored.     

单壁碳纳米管储氢研究

利用Gaussian03程序计算出C-H键的键能是1.88 eV,键长是0.113 nm.已知H-H键能是4.748 eV,键长是0.074 nm.显然,H-H键能大于C-H键的键能,所以在常温常压下碳纳米管储氢时,以物理吸附H_2分子为主,化学形式的C-H键吸附为辅.另外,利用LJ势能函数,计算了H_2分子在碳纳米管中C原子所成的六边形中心正上方、C原子正上方以及相邻两C原子中间正上方时H_2分子与碳纳米管之间的势能.得到无论H_2分子是被吸附到管内或管外,还是被吸附到中间区域或两端区域,都是H_2分子在C原子所成的六边形中心正上方时能量最低.当H_2分子被吸附到碳纳米管中间区域时,管内和管外的H_2分子距管壁的距离分别是0.320 nm和0.309 nm;而当H_2分子被吸附到碳纳米管两端区域时,这两个距离分别是0.324 nm和0.313 nm.     

单壁碳纳米管储氢研究

摘要 利用Gaussian03程序计算出C-H键的键能是1.88eV，键长是0.113nm。已知H-H键能是4.748eV，键长是0.074nm。显然， H-H键能大于C-H键的键能，所以在常温常压下碳纳米管储氢时，以物理吸附H2分子为主，化学形式的C-H键吸附为辅。另外，利用LJ势能函数，计算了H2分子在碳纳米管中C原子所成的六边形中心正上方、C原子正上方以及相邻两C原子中间正上方时H2分子与碳纳米管之间的势能。得到无论管内、管外或者两端，都是H2分子在C原子所成的六边形中心正上方时能量最低。且在管内时H2分子距离管壁的距离是0.320nm，在管外时距离管壁的距离是0.309nm；在两端的管内时距离管壁的距离是0.324nm，在两端的管外时距离管壁的距离是0.313nm。     

On the compressive response of carbon nanotube tangles

The nonlinear bulk compressibility of entangled multiwalled carbon nanotubes is studied. The analogy with textile fibre assemblies is explored by means of the well established van Wyk model. In view of the small diameter of the nanotubes, the possible effect of adhesive van der Waals interactions at tube-tube contacts is analysed. It is found, however, that the contribution of adhesive contacts to the bulk stress should be negligible. Compression experiments are performed on multi-walled carbon nanotubes and show that van Wyk's model is able to describe the response, although the values of the dimensionless parameter k of van Wyk's model were lower than expected. There is indeed no indication that van der Waals interactions play any significant role.     

Surfactant-assisted reflux synthesis, characterization and formation mechanism of carbon nanotube/europium hydroxide core-shell nanowires

Carbon nanotube (CNT)/europium hydroxide core-shell nanowires were prepared easily on a large scale under the boiling reflux of water assisted by the surfactant, sodium polystyrenesulfonate (SPS). The core-shell nanowires are characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectrum. A possible formation mechanism has been suggested as follows: The phenyl rings of SPS can react with the carbon ring of CNTs to form the π-π noncovalent bond, which makes the SPS cover the surface of CNTs entirely, and thus the surface of modified CNTs is negatively charged, which repel with each other resulting in the good dispersion. In addition, the negatively charged surface of CNTs adsorbs europium ions (positive). The adsorbed europium ions in situ react with OH⁻ ions to create europium hydroxide nanoparticles, and subsequently, the nanoparticles fuse together to form a dense coating layer on CNTs.     

Fabrication and electrochemical properties of free-standing single-walled carbon nanotube film electrodes

An easily manipulative approach was presented to fabricate electrodes using free-standing single-walled carbon nanotube (SWCNT) films grown directly by chemical vapor deposition.Electrochemical properties of the electrodes were investigated.In comparison with the post-deposited SWCNT papers,the directly grown SWCNT film electrodes manifested enhanced electrochemical properties and sensitivity of sensors as well as excellent electrocatalytic activities.A transition from macroelectrode to nanoelectrode behaviours was observed with the increase of scan rate.The heat treatment of the SWCNT film electrodes increased the current signals of electrochemical analyser and background current,because the heat-treatment of the SWCNTs in air could create more oxide defects on the walls of the SWCNTs and make the surfaces of SWCNTs more hydrophilic.The excellent electrochemical properties of the directly grown and heat-treated free-standing SWCNT film electrodes show the potentials in biological and electrocatalytic applications.     

Towards the mechanism of electrochemical hydrogen storage in nanostructured carbon materials

The mechanism of electrochemical hydrogen storage in a nanostructured carbon electrode using the electrodecomposition of KOH and H₂SO₄ aqueous solutions has been investigated by means of galvanostatic and voltammetry techniques. The role of charging the electrical double layer is carefully considered during the process of hydrogen insertion and deinsertion into carbon, i.e. electroreduction and electrooxidation, respectively. Once the electrode potential becomes lower than the equilibrium potential, hydrogen in the zero oxidation state is formed by the reduction of water in alkaline solution or the reduction of hydronium ions H₃O⁺ in acidic medium. In the next step, hydrogen is physically adsorbed (H_ad) onto the carbon surface and diffuses into the bulk of the carbon material with an efficiency which depends on the type of electrolyte. A higher amount of hydrogen is stored using the KOH medium, and the galvanostatic oxidation shows a well-defined plateau around -0.5 V vs. Normal Hydrogen Electrode (NHE). Due to the high overvoltage value in KOH (=0.55 V), the recombination steps of H_ad leading to molecular hydrogen evolution through the chemical (Tafel) or electrochemical (Heyrovsky) reactions are less favoured than in an H₂SO₄ medium (=0.32 V). Hence, a meaningful sorption of hydrogen is observed only in the basic electrolyte which shows a reversible capacity of 350 mAh/g (i.e. 1.3 wt.%) with a good electrical efficiency. Such performance demonstrates that nanostructured activated carbons might be a promising alternative to metallic alloys for electrochemical hydrogen storage. PACS 82.45.Yz; 81.05.Uw; 82.30.Rs; 82.45.Hk; 82.45.Fk; 81.05.Rm     

Single-walled carbon nanotube formation with double laser vaporization technique

Single-walled carbon nanotubes (SWNTs) were prepared with double laser vaporization of a graphite target and a metal/alloy target inside an electric furnace at 1200 ^°C ambient temperature with 500 torr Ar gas atmosphere. Each target was vaporized simultaneously with a different Nd:YAG laser. Several kinds of metal/alloy target (Ni, Co, Fe, and permalloy) were tested in order to see the difference in the resulting SWNT yield and the diameter distribution of them. The Raman spectra of SWNT-containing soot prepared by use of this technique with permalloy/carbon system indicated that permalloy gives almost the same yield as compared with Ni/Co carbon composite rod with single laser vaporization technique, though the diameter distribution of them is slightly different. Also, time-resolved images of the plume by carbon and permalloy nanoparticles after laser vaporization were collected using a high-speed video camera. These images suggest that the hot plumes due to carbon and permalloy nanoparticles do not mix together so extensively, at least in a few hundred microseconds after laser vaporization. The effect of time delay between two laser pulses on the yield and the diameter distribution of SWNTs was also presented and discussed.     

Rapid microwave-assisted synthesis and electrochemical characterization of gold/carbon nanotube composites

Hybrid nanostructures composed of gold nanoparticles (NPs) and carbon nanotubes (CNTs) have been prepared by a microwave-assisted method in the mixed solvents of oleylamine and oleic. The morphology, structure and composition of as-obtained Au/CNT composites are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD). The composites show characteristic plasmon absorption of Au NPs in the Ultraviolet–visual spectrum. Fourier transform infrared spectrum shows the successful introduction of functional groups on the surface of CNTs, which are crucial factors to assist the nucleation in situ of Au NPs on the surface of CNTs. Electrochemical measurements show the enhancement electrochemical response for the gold electrode modified with Au/CNT composites.     

On the role of relaxation processes in the acoustic mechanism of supramolecular structure formation in nematic liquid crystals

We have for the first time developed and tested a model constructed on the basis of nonequilibrium hydrodynamics and postulating that the structural relaxation processes of a nematic liquid crystal (NLC) in wave fields are important for the formation of supramolecular structures in the form of a system of linear domains in a planar mesophase layer. Distortions in the macrostructure of an NLC layer in the field of longitudinal waves were observed in the frequency range of 0.9–18.9 MHz. The values of the spatial period of domains at the threshold of the effect and the threshold amplitudes of the vibrational speed were determined for 10–300-μm-thick layers in wave fields with different degrees of uniformity for the temperature range where the mesophase exists. The simulation results are compared to experimental data.     

Single-walled carbon nanotube formation on iron oxide catalysts in diffusion flames

Single-walled carbon nanotubes (SWCNTs) are shown to grow rapidly on iron oxide catalysts on the fuel side of an inverse ethylene diffusion flame. The pathway of carbon in the flame is controlled by the flame structure, leading to formation of SWCNTs free of polycyclic aromatic hydrocarbons (PAH) or soot. By using a combination of oxygen-enrichment and fuel dilution, fuel oxidation is favored over pyrolysis, PAH growth, and subsequent soot formation. The inverse configuration of the flame prevents burnout of the SWCNTs while providing a long carbon-rich region for nanotube formation. Furthermore, flame structure is used to control oxidation of the catalyst particles. Iron sub-oxide catalysts are highly active toward SWCNT formation while Fe and Fe₂O₃ catalysts are less active. This can be understood by considering the effects of particle oxidation on the dissociative adsorption of gas-phase hydrocarbons. The optimum catalyst particle composition and flame conditions were determined in near real-time using a scanning mobility particle sizer (SMPS) to measure the catalyst and SWCNT size distributions. In addition, SMPS results were combined with flame velocity measurement to measure SWCNT growth rates. SWCNTs were found to grow at rates of over 100 μm/s.     

Synthesis, characterization and electrochemical behavior of polypyrrole/carbon nanotube composites using organometallic-functionalized carbon nanotubes

Thorn-like, organometallic-functionalized carbon nanotubes were successfully developed via a novel microwave hydrothermal route. The organometallic complex with methyl orange and iron (III) chloride served as reactive seed template, resulting in the oriented polymerization of pyrrole on the modified carbon nanotubes without the assistance of other oxidants. Morphological and structural characterizations of the carbon nanotube/methyl orange-iron (III) chloride and polypyrrole/carbon nanotube composites were examined using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), infrared spectroscopy and X-ray diffraction (XRD). The electrochemical property of the polypyrrole/carbon nanotube composite was elucidated by cyclic voltammetry and galvanostatic charge-discharge. A specific capacitance of 304 F g⁻¹ was obtained within the potential range of −0.5-0.5 V in 1 M KCl solution.     

Quantum-mechanical investigation of field-emission mechanism of a micrometer-long single-walled carbon nanotube

A quantum-mechanical simulation is carried out to investigate the charge distribution and electrostatic potential along a 1 microm long (5,5) single-walled carbon nanotube under realistic field-emission experimental conditions. A single layer of carbon atoms is found sufficient to shield most of the electric field except at the tip where strong field penetration occurs. The penetration leads to a nonlinear decrease of potential barrier for emission, which is equally responsible for the low threshold voltage besides the well-known geometrical field enhancement factor.