A parametric study of the large scale production of multi-walled carbon nanotubes by fluidized bed catalytic chemical vapor deposition

A parametric study investigating the impact of temperature, run duration, total pressure, and composition of the gaseous phase on the catalytic growth of multi-walled carbon nanotubes (MWCNT) has been performed. MWCNTs have been produced very selectively on the multi-gram scale by catalytic chemical vapor deposition from ethylene in a fluidized bed reactor. The kinetics of MWCNTs growth is fast and, with the catalyst used, no induction period has been observed. The kinetic law is of positive order in ethylene concentration and the process is limited by internal diffusion in the porosity of the catalyst. The formation of MWCNTs in the macroporosity of the catalyst induces an explosion of the catalyst grains. Such a process, thanks to the absence of temperature gradient and to the efficient mixing of the grains allows a uniform and selective treatment of the catalyst powder leading to very high selectivity towards MWCNTs formation. High purity MWCNTs have been obtained after catalyst dissolution. Depending on the temperature of production, the specific surface area of this material ranged between 95 and 455 m²/g.     

Narrow multi-walled carbon nanotubes produced by chemical vapor deposition using graphene layer encapsulated catalytic metal particles

The use of graphene layer encapsulated catalytic metal particles for the growth of narrower multi-walled carbon nanotubes (MWCNTs) has been studied using plasma-enhanced chemical vapor deposition and conventional thermal CVD. Ni–C or Fe–C composite nanoclusters were fabricated using the dc arc discharge technique with metal–graphite composite electrodes carrying a current of 100–200 A in a stainless-steel chamber filled with He and CH₄ mixture gas at 27 kPa. Nano-sized grains with diameters less than 10 nm were fabricated and deposited on a Si substrate, and were used as a catalyst for MWCNT growth. Structural analyses of the composite nanoclusters and MWCNTs were carried out using transmission electron microscopy. The results show that the diameters of the MWCNTs were reduced from 50–100 nm for a conventional Ni thin film-evaporated Si substrate to a minimum of roughly 2–4 nm in the present study.     

Synthesis of multi-walled carbon nanotubes by catalytic chemical vapor deposition using Cr2 − xFexO3 as catalyst

Chromium oxide and iron oxide solid solution was used as a catalyst for multi-walled carbon nanotubes synthesis by the catalytic chemical vapor deposition technique. The catalyst was prepared by the solution combustion synthesis method. Natural gas (NG) was employed as a carbon source for the carbon nanotube growth instead of methane, which is typically used. The carbon nanotube synthesis was carried out under H₂/NG and Ar/NG atmospheres at 950 °C. The Cr_2 − xFe_xO₃ catalyst was capable to produce carbon nanotubes only in H₂/NG atmospheres. Partial elimination of the catalyst after the synthesis was possible using a concentrated solution of HNO₃.     

Optimizing substrate surface and catalyst conditions for high yield chemical vapor deposition grown epitaxially aligned single-walled carbon nanotubes

Single-crystal stable-temperature (ST)-cut quartz substrates, which have a (0 1 1 1) crystallographic plane with their surface normal lying close to 38° from the y axis ([0 1 0]), were annealed in air prior to use as a support for aligned carbon nanotube growth by chemical vapor deposition. Very smooth substrate surfaces were obtained with annealing times in the vicinity of 15 h at a temperature of 750 °C. These smooth surfaces are ideal for the growth of horizontally aligned SWCNTs with high spatial density, while less dense SWCNTs were obtained with less smooth surfaces. Under optimized growth conditions, only SWCNT are observed and they can grow to lengths in excess of 100 μm. Our findings suggest structural defects interfere with the growth process. A binary Fe/Co catalyst was employed to grow the nanotubes. No obvious dependence on the Fe:Co ratio is observed.     

Removal of entrapped iron compounds from isothermally treated catalytic chemical vapor deposition derived multi-walled carbon nanotubes

Compositional changes of the residual iron compounds in isothermally treated catalytic chemical vapor deposition derived multi-walled carbon nanotubes have been monitored using ⁵⁷Fe transmission Mössbauer spectroscopy and X-ray fluorescence. The iron phases entrapped in the as-synthesized carbon nanotubes consist of γ-iron, α-iron, Fe₃C and Fe_1−xS. The Fe_1−xS phase decomposes completely around 1500 °C while the iron carbide phase decomposes in the temperature range of 1500-2400 °C. The obtained apparent activation energy of ca. 76 kcal/mol suggests that the entrapped iron was removed via a diffusion process during thermal treatment.     

Dynamics of catalyst particle formation and multi-walled carbon nanotube growth in aerosol-assisted catalytic chemical vapor deposition

In aerosol-assisted catalytic chemical vapor deposition (CCVD), the catalyst and carbon precursors are introduced simultaneously in the reactor. Catalyst particles are formed in situ and aligned multi-walled CNTs grow at a high rate. To scale-up the process, it is crucial to understand the chemical transformation of the precursors along the thermal gradient of the reactor, and to correlate nanotube growth with catalyst nanoparticle formation. The products synthesized along a cylindrical CVD reactor from an aerosol composed of ferrocene and toluene, as catalyst and carbon precursor, respectively, were studied. The product surface density and iron content are determined as a function of the location and the iron vapor pressure in the reactor. Samples are analyzed by electron microscopy, X-ray diffraction and Raman spectroscopy. We show the strong influence of the thermal gradient on location and rate of formation of both iron particles and CNTs, and demonstrate that catalyst particles are formed by gas phase homogeneous nucleation with a size which correlates with iron vapor pressure. They are gradually deposited on the reactor walls where nanotubes grow with an efficiency which is varying linearly with catalyst particle density. CNT crystallinity appears very high for a large range of temperature and iron content.     

Self-assembling of multi-walled carbon nanotubes on a porous carbon surface by catalyst-free chemical vapor deposition

Synthesis of carbon nanotubes (CNTs) by catalyst-free chemical vapor deposition (CFCVD) is one of the most important challenges in nanotube science. Self-assembling multi-walled CNTs (MWCNTs) were produced on a porous carbon surface using carbon black (CB) as a substrate, at 800 °C by the decomposition of diluted ethylene. MWCNTs with an outer-diameter distribution of 20–80 nm, examined by scanning and transmission electron microscopy, could be self-assembled on pore structures of CB surface by CFCVD.     

CVD法制备碳纳米管的催化剂研究

CVD法制备单壁碳纳米管时有几个不可忽略的影响因素,其中催化剂的选取与制备极为重要,许多研究者采用不同的催化剂,获得了不同产量与质量的碳纳米管。本文主要从催化剂的选取和制备方法入手,综述了催化剂对碳纳米管制备的影响。     

Coiled carbon nanotubes growth via reduced-pressure catalytic chemical vapor deposition

Coiled carbon nanotubes were prepared by catalytic chemical vapor deposition (CCVD) on finely divided Co nano-particles supported on silica gel under reduced pressure and relatively low gas flow rates. The morphology and the graphitization of the coil tube, coil bend, and coil node of the coiled carbon nanotubes were examined by transmission electron microscope (TEM). The influence of pH value, reaction pressure, and flow rate of C₂H₂ on the growth of the coiled carbon nanotubes were also discussed. With the drastic reduction in the consumption of C₂H₂ and lower required pressure with the modified CCVD approach, the amount of amorphous carbon coated on the carbon nanotubes was shown to be greatly reduced. Most importantly, this method offers a preferable alternative for the efficient, environment-friendly and safer growth of coiled carbon nanotubes.     

Intermetallic catalyst for carbon nanotubes (CNTs) growth by thermal chemical vapor deposition method

The methane conversion and carbon yield of the chemical vapor deposition (CVD) reaction suggests that the optimum reaction conditions of the formation of multi-wall carbon nanotubes (MWCNTs) can be obtained by using a 50 mg of nano-MgNi alloy under pyrolysis of the pure CH₄ gas with the flow rate about 100-120 cm³/min at 650 °C for 30 min. Raman results indicate the CNTs are in multi-wall structure, since no single-wall characteristic features appearing in the 200-400 cm⁻¹ region. This is consistent with those of the XRD and TGA findings. Under selected condition, the carbon yield and the CNTs purity can reach up to 1231% and 92% in the presence of hydrogen. It is presumable that the presence of hydrogen in the pyrolysis of CH₄ prevents the deactivation of catalysts and enhances the graphitization degree of CNTs. In addition, the presence of Mg metal in the alloy can prevent the aggregation of the Ni metal and forms the active Mg₂Ni phase to enhance the CH₄ pyrolysis to form CNTs. After the purification procedures with both air oxidation at 550 °C and HCl treatments, the final purified yield and purity of CNT reach to 73.2% and (98.04 ± 0.2)% respectively.     

化学气相沉积法制备碳纳米管的研究进展

从催化剂、碳源气体及反应器的选择等方面综述了化学气相沉积法制备碳纳米管的研究进展 ,讨论了碳纳米管的合成机理。指出催化合成碳纳米管的研究难点在于管径的有效调控和大批量生产 ,今后的研究方向应为单层碳纳米管的有效合成     

Vertically-aligned carbon nanotubes prepared by water-assisted chemical vapor deposition

Vertically-aligned single walled carbon nanotubes (V-SWNTs) were prepared by water-assisted and ethylene-pyrolyzing chemical vapor deposition. Water vapor was introduced into the growth environment by passing a small fraction of Ar carrier gas through a water bubbler. The effects of processing gas flow rate, growth time, and water vapor content on the growth of SWNTs using Mo/Fe as the catalyst were systematically studied. For the catalyst of SWNTs growth, multi-metal layers consisting of an Al underlayer with 10 nm in thickness and Mo/Fe layers on top were deposited onto the silica film. Evidences of V-SWNTs with high-purity were found by Raman spectroscopy and TEM morphology. The trace amount of water vapor enhanced the activity of metal catalysts to further assist the growth of SWNTs. For the Mo (0.5 nm)/Fe (1 nm) structure, V-SWNTs grew from surface when the growth time lasted 10 min shown in SEM diagram meanwhile the portion of SWNTs increased until 30 min and then a layer of SWNTs developed shown in the RBM peak in the Raman spectra.     

Synthesis of carbon nanotubes on graphene quantum dot surface by catalyst free chemical vapor deposition

The growth of carbon nanotubes (CNTs) on graphene quantum dot surface has been explored using acetylene as the carbon source in a catalyst free chemical vapor deposition process. Dynamic studies were conducted to observe the CNT growth. The obtained nanotubes have a diameter distribution of 10–30 nm and show medium graphitic quality. Transmission electron microscopy observations and dynamic studies indicate that the formation of CNTs follows a different mechanism from traditional growth models, in which a wire-to-tube process and self-assembling of CNTs are involved. On the basis of these observations, a tentative continuous growth model is proposed for the CNT growth.     

Origin of radial breathing mode in multiwall carbon nanotubes synthesized by catalytic chemical vapor deposition

The origin of radial breathing mode (RBM) in the Raman spectra of multiwall carbon nanotubes (MWNCTs) is discussed. In general, RBM is characteristics of single wall carbon nanotube (SWCNT). With the help of transmission electron microscope (TEM) and Raman spectroscopic studies, it is established that the presence of SWCNT in the cavity of MWCNT is responsible for the appearance of RBM in MWCNT (synthesized by low temperature catalytic chemical vapor deposition technique). The estimated diameter of 8.2 Å (from Raman study) of SWCNT is almost same as that observed (∼8.3 Å) in TEM studies.     

Growth of carbon nanotubes by open-air laser-induced chemical vapor deposition

Carbon nanotubes have remarkable mechanical, electronic and electrochemical properties, but the full potential for application will be realized only if the growth of high quantity and quality carbon nanotubes can be optimized and well controlled. In this study, carbon nanotubes have been successfully grown on fused quartz rods by a novel open-air laser-induced chemical vapor deposition (LCVD) technique with gold palladium nanoparticles as catalyst material. In this LCVD technique, a curtain of inert nitrogen gas was used to shield the deposition zone from the surrounding environment and allows the growth of the nanotubes to occur under open-air conditions. A 35-W continuous CO₂ laser was used as a heat source to induce a local temperature rise on the substrate surface covered with metal nanoparticles, subsequently resulting in deposition of multi-wall carbon nanotubes. The carbon nanotubes deposited in this study are derived from a precursor mixture that consists of propane and hydrogen, and are in tangled form with different diameters (10-250 nm) and structures. Raman spectroscopy, transmission and scanning electron microscopy are used to investigate the microstructure and composition of the carbon nanotubes.     

Mass production of aligned carbon nanotube arrays by fluidized bed catalytic chemical vapor deposition

A parametric study investigating the impacts of loading amount of active phase, growth temperature, H₂ reduction, space velocity, and apparent gas velocity on the intercalated growth of vertically aligned carbon nanotube (CNT) arrays among lamellar catalyst was performed. A series of Fe/Mo/vermiculite catalysts with Fe/vermiculite ratio of 0.0075-0.300 were tested. Metal particles were dispersed among the layers of vermiculite after H₂ reduction. Uniform catalyst particles, with a size of 10-20 nm and a density of 8.5 × 10¹⁴ m⁻², were formed among the vermiculite layers at 650 °C. CNTs with high density synchronously grew into arrays among the vermiculites. With the increasing growth temperature, the alignment of CNTs intercalated among vermiculites became worse. Moreover, intercalated CNTs were synthesized among vermiculite layers in various flow regimes. The as-grown particles were with a size of 1-2 mm when the fluidized bed reactor was operated in particulate fluidization and bubbling fluidization, while the size of the as-grown products decreased obviously when they grown in the turbulent fluidized bed. Based on the understanding of the various parameters investigated, 3.0 kg/h of CNT arrays were mass produced in a pilot plant fluidized bed reactor.