Formation and Yield of Multi-Walled Carbon Nanotubes Synthesized via Chemical Vapour Deposition Routes Using Different Metal-Based Catalysts of FeCoNiAl,CoNiAl and FeNiAl-LDH

Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.     

The synthesis and characterization of carbon nanotubes grown by chemical vapor deposition using a stainless steel catalyst

Multi wall carbon nanotubes (MWCNTs) were grown on a stainless steel (SS) sheet by chemical vapor deposition without the addition of external metal catalyst. We found that the key for highly efficient growth includes the nanoscale roughness of the SS surface, as shown by scanning tunneling microscopy, that acts as catalyst/template in the nanotube formation. Raman spectroscopy and electron microscopy were used to check the nature and quality of the synthesized nanotubes. We conclude that stainless steel favors a base-growth mechanism. Transmission electron energy loss spectroscopy performed on single metallic particles found inside the nanotubes clarified the atomic nature of the catalytic particles supplied by the steel. Only unoxidized iron was found and no traces of nickel and chromium were detected. In addition, the SS substrate has been used for a second growth process after carefully removing the synthesized CNTs, proving that a continuous production of CNTs from the same substrate is achievable.     

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 carbon nanotubes filled with Fe3C nanowires by CVD with titanate modified palygorskite as catalyst

Multi-walled carbon nanotubes (MWCNTs) have been successfully synthesized with titanate-modified palygorskite as catalyst and acetylene as carbon source by chemical vapor deposition (CVD) at high temperature. Transmission electron microscopy (TEM) studies showed that there were a lot of carbon nanotubes partially filled with elongated foreign material in their inner cavities. X-ray energy dispersive spectrum (EDS) analyses and selected area electron diffraction (SAED) investigations on the encapsulated material revealed that it was single crystalline iron carbide (Fe₃C) derived from ferric precursors in the mineral. The yield of carbon nanotubes was influenced by preparation temperature based on thermal gravimetric analyses (TGA). The relative quantity of Fe₃C nanowires was influenced by the temperature and the local structure of nanotubes upon TEM observations. A growth mechanism is also proposed in the paper.     

Lithographically defined site-selective growth of Fe filled multi-walled carbon nanotubes using a modified photoresist

Partially Fe filled multi-walled carbon nanotubes (MWCNTs) were grown by chemical vapor deposition with propane at 850 °C using a simple mixture of iron (III) acetylacetonate (Fe(acac)₃) powder and conventional photoresist. Scanning electron microscopy revealed that catalytic nanoparticles with an average diameter of 70 nm are formed on the Si substrate which governs the diameter of the MWCNTs. Transmission electron microscopy shows that the nanotubes have a multi-walled structure with partial Fe filling. A site-selective growth of partially Fe filled MWCNTs is achieved by a simple photolithographic route.     

Growth mechanism of vapor phase CVD-grown multi-walled carbon nanotubes

The formation mechanisms involved in the growth of carbon nanotubes (CNTs) by spray pyrolysis was studied. Both iron and nickel were used as catalysts for growth, and nanotubes were also produced using thermal chemical vapor deposition for comparison. Transmission electron microscopy was used to analyze the encapsulated metal catalyst particles found within the tubes, and the dimensions and location of these particles was recorded. CNTs grown by spray pyrolysis were found to have encapsulated particles in both the middle and end of tubes, with large length to diameter ratios. As a result of these observations, it is concluded that nanotubes grown using spray pyrolysis are formed via an open-ended, root growth mechanism. Additionally, the presence of multiple, high aspect ratio particles within single tubes is explained by an additional growth theory. During the continued growth of these CNTs, metal atoms or nanoscale metal catalyst particles deposit in the open ends of growing tubes, forming new particles and helping to prevent tube closure. CNTs grown with thermal CVD did not contain similar elongated particles or particles along the middle of the tubes, indicating that this new growth mechanism is only applicable in the case of tubes grown via spray pyrolysis or other vapor phase CVD growth methods.     

Effects of catalyst pre-treatment on the growth of single-walled carbon nanotubes by microwave CVD

Layers of carbon nanotubes were deposited by microwave CVD on oxidized silicon substrates coated with Al-Fe-Mo catalyst films. To achieve a tube growth at about 973 K, the ion bombardment of the catalyst surface has to be avoided. The appropriate pre-treatment of the substrates is essential for the deposition of single-walled carbon nanotubes. Annealing in air is preferable to the frequently used reducing pre-treatment prior to the deposition as a higher area density of the tubes and a better reproducibility of deposition can be obtained. To figure out this finding, selected samples were investigated by analytical transmission electron microscopy and Raman spectroscopy. It is shown that the pre-treatment has a strong effect on the size and distribution of the catalyst particles.     

Single-step synthesis of germanium nanowires encapsulated within multi-walled carbon nanotubes

We report the single-step synthesis of Ge nanowires encapsulated within multi-walled carbon nanotubes (MWCNTs) from a phenyltrimethylgermane (C₆H₅Ge(CH₃)₃) precursor, using a simple chemical vapor deposition (CVD) method. The MWCNT/germanium nanowires were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) measurements. TEM analysis reveals that the nanowires consist of well crystallized Ge cores which are completely encapsulated by the sheath-like MWCNTs, the latter corresponding to a layer thickness of 5-10 nm. SEM images, corresponding to various stages of nanowire growth, indicate that MWCNT growth occurs at Ge nanoparticles and that the growing MWCNTs carry Ge as nanowires away from the nanoparticles. By optimizing the CVD parameters, nanowires can be produced with uniform length and diameter in the range 6-10 μm and 200-300 nm, respectively.     

Hydrogen sulfide sensing properties of multi walled carbon nanotubes

This paper investigates the effect of functional groups on the hydrogen sulfide sensing properties of multi-walled carbon nanotubes using carboxyl and amide groups and Mo and Pt nanoparticles as decorated precursors in gaseous state at working temperature. Carbon nanotubes were synthesized by the CVD process and decorated with the nano particles; provide higher sensitivity for H₂S gas detection. The MWCNTs were characterized by scanning electron microscopy combined with energy dispersive X-ray (SEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ATR-IR absorption and Fourier transforms infrared (FT-IR) analyses. The MWCNTs were deposited as a thin film layer between prefabricated gold electrodes on alumina surfaces. The sensitivity of carbon nanotubes was measured for different H₂S gas concentrations and at working temperature. The results showed that the measured electrical conductance of the modified carbon nanotubes with functional groups is modulated by charge transfer with P-type semiconducting characteristics and metal decorated carbon nanotubes exhibit better performances compared to functional groups of carboxyl and amide for H₂S gas monitoring at room temperature.     

Catalyst‐Assisted Growth of Single‐Crystalline Hafnium Carbide Nanotubes by Chemical Vapor Deposition

Single‐crystalline hafnium carbide (HfC) nanotubes were synthesized by a one‐step catalyst‐assisted chemical vapor deposition (CVD) method. The typical nanotubes had uniform diameters of ~60 nm and wall thicknesses of ~15 nm and preferentially grew along [201]. From HRTEM/EELS analysis, the growth mechanism based on carbon nanotubes (CNT) tip growth and CNT‐templated reaction was proposed for explaining the formation of HfC nanotubes. According to the mechanism, CNTs were first formed by diffusion of C atoms on the surface of solid Ni catalyst particles. Then, gaseous Hf species reacted with C atoms from CNTs to form HfC nanotubes. During the entire growth process, Hf atoms did not participate in the catalytic reaction. Thus, this process was distinguished from the conventional vapor–liquid–solid process.     

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.     

Catalytic formation of carbon phases in metal modified, porous polymer derived SiCN ceramics

A novel method for the simultaneous formation of catalytic active metal nanoparticles, multiwall carbon nanotubes (MWCNTs) and/or turbostratic carbon and porous M@SiCN (M = Fe, Co, Pt, Cu, Ag, Au) ceramics during pyrolysis of metal modified polysilazanes and polyethylene (PE) particles as sacrificial filler is described. The thermal decomposition of the polyethylene leads not only to the generation of the porosity but also to an in situ reduction of the metal compounds to the metal nanoparticles, due to the reductive atmosphere. Depending on the metal, carbon nanotubes as well as turbostratic carbon were formed in different amounts, due to the chemical vapor deposition (CVD) like conditions. The resulting carbon phases, ceramics and metal nanoparticles were investigated using the combination of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) measurements, giving evidence for the presence of the carbon phases and the metal particles.     

Platelet-like catalyst design for high yield production of multi-walled carbon nanotubes by catalytic chemical vapor deposition

We investigated the effect of catalyst design on the synthesis of multi-walled carbon nanotubes (MWCNTs) by chemical vapor deposition (CVD). A set of highly active supported sol–gel Co–Mo/MgO and Ni–Mo/MgO catalysts was prepared systematically modifying the calcination temperature. First, the evolution of catalysts’ crystallographic phases and their morphology were studied by X-ray diffraction (XRD), Raman spectroscopy, scanning electron (SEM) and transmission electron (TEM) microscopy. Second, the catalysts were used for the CVD growth of MWCNTs. The resulting materials were analysed by SEM and TEM, Raman and XRD to establish a relation between catalyst design and MWCNT yield. We show that our catalyst synthesis route leads to the formation of laminar non-porous catalyst systems, which at a calcination temperature of 800 °C stabilize in a crystallographic phase of Me_xMg_1−xMoO₄ (Me = Co or Ni). We give evidence that increased MWCNT yields of more than 3000 wt.% with respect to the catalysts are directly related to the aforementioned crystallographic phase. Finally, we propose a growth model based on the continuous exfoliation of platelet-like catalyst systems. This consistently explains the high catalytic activity towards MWCNT production using a non-porous catalyst. Our findings provide important insights for catalyst design strategies towards large-scale MWCNT production.     

Formation of gold nanoparticles on multiwalled carbon nanotubes by thermal evaporation

Multiwalled carbon nanotubes (MWCNTs) were grown on W substrates by chemical vapor deposition and modified with Au nanoparticles by thermal evaporation. The resulting hybrid structures were investigated by TEM to determine the effects of evaporation rate, nominal film thickness, and substrate temperature on the nanoparticle size and distribution. The results demonstrate that as-grown MWCNTs can be used as a support for well distributed Au nanoparticles, with the size and distribution on the carbon nanotubes being primarily influenced by the nominal film thickness. The observed structures ranged from small 4 nm diameter spherical particles to 150 nm long wire-like structures. Depositions with substrates at 25 °C and 400 °C resulted in similar particle structures, except for the highest amount of deposited Au.     

Scaled-up self-assembly of carbon nanotubes inside long stainless steel tubing

The self-assembly of carbon nanotubes (CNTs) on the inside wall of a relatively long stainless steel tubing for applications such as separations and chromatography, is reported in this paper. The CNTs were deposited by the chemical vapor deposition (CVD) using ethylene as the carbon source and the iron nanostructures in the stainless steel as the catalyst. The coating consisted of a layer of CNTs aligned perpendicular to the circumference of the tubes, often with an overcoat of disordered carbonaceous material, which could be selectively oxidized by exposing the CNT layer below to pure O₂ at 375 °C. Variation in uniformity in terms of the thickness and morphology of the deposited film and surface coverage were studied along the length of a tube by scanning electron microscopy (SEM). The effects of process conditions, such as flow rate and deposition time on the coating thickness, were studied. The catalytic effect of the iron nanostructures depended on surface conditioning of the tubing. It was found that the pretreatment temperature influenced the quality of the nanotube coating. The morphology of the CNT deposit supported the base-growth scheme and VLS (vapor-liquid-solid) growth mechanisms of CNTs.     

Influence of the nanostructure of silica supports on the growth and morphology of MWCNTs synthesized by CCVD method

Due to the influence of its superficial physical parameters on the interaction with catalyst, mesoporous silica is commonly referred as suitable support to grow carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CCVD) method. Faced with the various possibilities of applying nanostructured SiO₂/CNTs composites, this work aims to evaluate and clarify the influence of the silica mesoporosity and morphology on the quality and amount of CNTs produced by CCVD process. Five different nanostructured silicas (n-SiO₂) were produced by sol-gel method. Basically, four silica samples were synthesized with the addition of an acidic catalyst and one with a basic catalyst. Thermogravimetric analysis, Raman spectroscopy, transmission electron microscopy and scanning electron microscopy were used to characterize the silica supports and the as-grown CNTs produced in this work. The obtained results show differences in the morphology of the synthesized CNTs according to the physical properties of each n-SiO₂. The mesoporous silica structure, due to different pore size distribution and volume, affected the interaction between the support and the catalyst, and, consequently, the quality and amount of the synthesized multi-walled carbon nanotubes (MWCNTs). Silica supports with either high mesopore volume, or high mesopore size, provide the highest quantities of as-grown CNTs materials. However, in terms of quality of as-grown CNTs, the supports with lower mesopores volume were more adequate to the MWCNTs synthesis. Nevertheless, the presence of pores with compatible size may have allowed an improved anchorage of catalyst particles inside these pores favoring the growth of CNTs with good quality.     

Parametric study of atmospheric-pressure single-walled carbon nanotubes growth by ferrocene–ethanol mist CVD

Uniform web-like films consisting single-walled carbon nanotubes (SWCNTs) were deposited on a silicon substrate using the chemical vapor deposition (CVD) of ferrocene–ethanol mist at atmospheric pressure (∼ 1 atm). The tiny mist was generated using a high-frequency ultrasonic vibration. The effects of various parameters including deposition position in the reactor, temperature, ferrocene/ethanol ratio, flow rate of carrier gas (argon), and deposition time on the formation of SWCNTs was investigated using high-resolution scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The worm region outside the furnace was found to be a suitable position for the formation of SWCNT films. The furnace temperature and the flow rate of carrier gas were found to determine the diameter and crystallinity of nanotube. The ferrocene concentration in ethanol strongly influenced the amount of impurity particles in the material. Moreover, the intensity of metallic tail in D-band was found to decrease with increasing the flow rate, showing a possibility of the formation of semiconducting SWCNTs. Results of this study can be used to improve understanding of the growth of SWCNTs by floating catalyst CVD of alcohol mist.     

Characteristics of graphene-layer encapsulated nanoparticles fabricated using laser ablation method

Graphene layer-encapsulated Ni nanoparticles with diameters between 3 and 10 nm were fabricated by laser ablation techniques and deposited directly on the Si substrate at room temperature. It was found from the field-emission type scanning electron microscopy (FE–SEM) and transmission electron microscopy(TEM) analyses that any carbon nanotubes were not fabricated in the deposited nano-materials. High-resolution TEM observation showed the core-shell structure of Ni–C particles with crystalline nickel core surrounded by graphite-like layers. The X-ray diffraction(XRD) pattern also revealed that nanoparticles embedded in graphene capsules are crystalline nickel. With these Ni–C nanoparticles, we demonstrated the growth of vertically aligned carbon nanotubes with low spatial density on a silicon substrate by thermal CVD.     

Nucleation of diamond over nanotube coated Si substrate using hot filament chemical vapor deposition (CVD) system

We studied the use of carbon nanotubes as a seeding layer for the nucleation of diamond on Si (100) substrate by using a hot filament chemical vapor deposition (HFCVD) system. Prior to deposition, substrates were seeded with multi-wall carbon nanotube (MWCNT) powder which was prepared separately. MWCNTs were used as nucleation precursors. The diamond grains grew essentially over the nanotubes with a higher growth density in comparison with the un-seeded substrates. The scanning electron microscopy (SEM) image of surface morphology shows crystallites of cauliflower shaped grains. The micro Raman spectroscopic results show a sharp peak at 1,332 cm^-1 corresponding to diamond phase. X-ray photoelectron spectroscopic study show the presence of carbon (C_1s) phase. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

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.