High growth of SWNTs and MWNTs from C2H2 decomposition over Co-Mo/MgO catalysts

A series of MgO supported catalysts having Co and Mo metals 5-40 wt.% in a ratio of 1:1 was prepared by impregnation method. Carbon nanotubes (CNTs) were grown over the catalysts by decomposition of C₂H₂ at 800 °C for 30 min. It was found that 5 and 10 wt.% Co-Mo/MgO catalysts produced single-wall nanotubes (SWNTs), whereas 20, 30 and 40 wt.% Co-Mo/MgO catalysts produced multi-wall nanotubes (MWNTs). The catalyst Mo/MgO was inactive in growing CNTs. In Co-Mo/MgO catalysts, however Mo generated a favorable environment to grow SWNTs. The growth of SWNTs was strongly dependent on the formation of small clusters of cobalt, which may generate from the decomposition of CoMoO₄ species during the nanotube growth. MWNTs were produced over comparatively larger cobalt clusters generated from Co₃O₄ phase during the nanotube growth stage. The yields of SWNTs were about 6% and 27% over 5 and 10 wt.% Co-Mo/MgO catalysts, respectively. MWNTs yield (576%) was observed over 40 wt.% Co-Mo/MgO catalyst. Carbon yield (%) highly varied with acetylene concentration.     

Catalytic effect of metal elements on the growth of GaN and Mg-doped GaN micro-crystals

Catalytic effect of metal elements was observed in the growth of GaN and Mg-doped GaN micro-crystals. High quality GaN micro-crystals were synthesized by direct reaction of gallium and ammonia using a Ni-mesh catalyst. Mg-doped GaN micro-crystals were also grown by the same reaction scheme in the presence of MgCl₂. The growth rate of GaN micro-crystals markedly increased in the presence of the catalyst. The average grain size of GaN microcrystals synthesized in the presence of Ni and Mg metals was larger than that in the absence of the metals. The characterization of the catalytically grown GaN micro-crystals using transmission electron microscopy and X-ray and/or electron diffraction pattern showed the growth of dislocation free hexagonal GaN micro-crystals. Photoluminescence (PL) and Catholuminescence (CL) measurements also showed the growth of good quality n-and p-type GaN microcrystals using Ni catalyst     

Effects of bimetallic catalyst composition and growth parameters on the growth density and diameter of carbon nanotubes

Multi-wall carbon nanotubes (MWNTs) were synthesized by catalytic decomposition of acetylene over Fe, Ni and Fe-Ni bimetallic catalysts supported on alumina under various controlled conditions. The growth density and diameter of CNTs were markedly dependent on the activation time of catalysts in H₂ atmosphere, reaction time, reaction temperature, flow rate of acetylene, and catalyst composition. Bimetallic catalysts were apt to produce narrower diameter of CNTs than single metal catalysts. For the growth of CNTs at 600 ‡C under 10/100 seem flow of C₂H₂/H₂ mixture, the narrowest diameter about 20 nm was observed at the reaction time of 1 h for 20Fe : 20Ni : 60Al₂O₃ catalyst, but at that of 1.5 h for 10Fe : 30Ni : 60Al₂O₃ catalyst. It was considered that the diameter and density of CNTs decreased with the increase of the growth time mainly due to hydrogen etching. The growth of CNTs followed the tip growth mode.     

Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron-nickel catalyst supported on alumina

Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over 40Fe:60Al₂O₃, 40Ni:60Al₂O₃ and 20Fe:20Ni:60Al₂O₃ catalysts. High density CNTs of 20 nm diameter were grown over the 20Fe:20Ni:60Al₂O₃ catalyst, whereas low growth density CNTs of 40 and 50 nm diameter were found over 40Fe:60Al₂O₃ and 40Ni:60Al₂O₃ catalysts. Smaller catalyst particles enabled the synthesis of highly dense, long and narrow-diameter CNTs. It was found that a homogeneous dispersion of the catalyst was an essential factor in achieving high growth density. The carbon yield and the quality of CNTs increased with increasing temperature. For the 20Fe:20Ni:60Al₂O₃ catalyst, the carbon yield reached 121% after 90 min at 700 °C. The CNTs were grown according to the tip growth mode. Based on reports regarding hydrocarbon adsorption and decomposition over different faces of Ni and Fe, the growth mechanism of CNTs over the 20Fe:20Ni:60Al₂O₃ catalyst are discussed.     

Fabrication of vertical GaN/InGaN heterostructure nanowires using Ni-Au bi-metal catalysts

We have fabricated the vertically aligned coaxial or longitudinal heterostructure GaN/InGaN nanowires. The GaN nanowires are first vertically grown by vapor–liquid-solid mechanism using Au/Ni bi-metal catalysts. The GaN nanowires are single crystal grown in the [0001] direction, with a length and diameter of 1 to 10 μm and 100 nm, respectively. The vertical GaN/InGaN coaxial heterostructure nanowires (COHN) are then fabricated by the subsequent deposition of 2 nm of In_xGa_1-xN shell on the surface of GaN nanowires. The vertical GaN/InGaN longitudinal heterostructure nanowires (LOHN) are also fabricated by subsequent growth of an InGaN layer on the vertically aligned GaN nanowires using the catalyst. The photoluminescence from the COHN and LOHN indicates that the optical properties of GaN nanowires can be tuned by the formation of a coaxial or longitudinal InGaN layer. Our study demonstrates that the bi-metal catalysts are useful for growing vertical as well as heterostructure GaN nanowires. These vertically aligned GaN/InGaN heterostructure nanowires may be useful for the development of high-performance optoelectronic devices.     

Low-Temperature Growth of Carbon Nanotubes on Bi- and Tri-metallic Catalyst Templates

Low temperature growth process of carbon nanotubes (CNTs) over bi-metallic (Co–Fe) and tri-metallic (Ni–Co–Fe) catalysts on Si/Al/Al₂O₃ substrates is carried out from acetylene precursor using hydrogen, ammonia or nitrogen as a carrier in a low pressure chemical vapor deposition system. Using the tri-metallic Ni–Co–Fe catalyst template, vertically aligned CNTs of ~700 nm length could be grown already at 450 °C within 10 min using ammonia as a carrier. Within the same period of time, on bi-metallic Co–Fe catalyst templates, ~250 nm long aligned nanotubes emerged already at 400 °C in nitrogen carrier. At low temperatures most of the catalyst materials were elevated from the support by the grown nanotubes indicating tip growth mechanism. The structure of catalyst layers and nanotube films was studied using scanning and transmission electron microscopy and atomic force microscopy.     

Thin film metallic catalyst coatings for the growth of multiwalled carbon nanotubes by pyrolysis of xylene

Thin film metallic coatings applied to alumina and silicon substrates are investigated for their use as a catalyst to help grow high-quality multiwall carbon nanotubes (MWNTs). Substrate coatings examined include Fe, Tb:Fe, Ni, Cu, and Ni:Fe, with xylene used as the hydrocarbon source. Coating the substrate with Tb₉₀Fe₁₀ and Ni₈₀Fe₂₀ facilitated dense and uniform growth of MWNTs without graphitic particles; Ni and Fe substrate coatings produced graphitic particles in addition to the MWNTs, while Tb and Cu were found to be completely inactive with no MWNT growth. Many of the MWNTs grown over Ni:Fe have a helical appearance, while the MWNTs grown over Tb₉₀Fe₁₀ did not contain catalyst particles     

Synthesis of carbon nanotubes over nickel–iron catalysts supported on alumina under controlled conditions

Carbon nanotubes (CNTs) were synthesized by catalytic decomposition of acetylene over Fe, Ni and Fe–Ni catalysts supported on alumina. The growth of CNTs was carried out at various reaction conditions. The growth density and diameter of CNTs could be controlled by varying the catalyst composition and the growth parameters. The growth density of CNTs increased with increasing the activation time of catalysts in H₂ atmosphere and/or decreasing acetylene concentration. At 600°C, higher density of CNTs was observed at 60 min for higher Fe containing catalyst, whereas at 90 min for higher Ni containing catalyst. The growth density of CNTs highly increased with increasing reaction time from 30 to 60 min. For all the catalysts, the diameter of CNTs decreased with increasing growth time further mainly due to hydrogen etching. Bimetallic catalysts produced narrower diameter CNTs than single metal catalysts. The growth of CNTs followed the tip growth mode and the CNTs were multi-walled CNTs.     

Characterization of single-wall carbon nanotubes by N2 adsorption

N₂ adsorption isotherms at 77 K of single-wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), and mixtures of these carbon nanotubes (CNTs) were analyzed for differences in their pore size distributions (PSDs). The PSDs, calculated in the microporous region by the Horvath–Kawazoe method and in the mesoporous region by the BJH method, are in agreement with the structures of both types of CNTs deduced from high-resolution transmission electron microscopy. A characteristic peak in the microporous region in the PSD of SWNTs is not present in the PSDs of MWNTs and impurities such as amorphous carbon, metal residues of catalysts, etc. The evaluation of this peak is proposed as a convenient tool for the quantitative characterization of SWNT purity in carbon nanotube-containing samples.     

Selective growth of horizontally-oriented carbon nanotube bridges on patterned silicon wafers by electroless plating Ni catalysts

The main purpose of this research was to develop an Integrated Circuit compatible process to grow the horizontally-oriented carbon nanotubes (CNTs) across the trenches of the patterned Si wafer, which was produced by conventional photolithography technique. The selectivity of the process is based on the difference in electrical conductivity between amorphous silicon (a:Si) and silicon nitride (Si₃N₄), where the catalyst can be much easier deposited by electroless plating on the a:Si part of the pattern. The selectivity is also based on greater chemical reactivity of the catalyst with a:Si to form silicides, instead of with Si₃N₄. Furthermore, the Si₃N₄ barrier layer of the pattern was designed on top of the a:Si layer to guide the growth of CNTs in horizontal direction to bridge the trenches of the pattern. The as-deposited catalysts were examined by Auger electron spectroscopy (AES). The catalyst-coated pattern was pretreated in hydrogen plasma and followed by CNT growth in a microwave plasma chemical vapor deposition (MPCVD) system. The CNT bridges were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and I–V measurements. Under the present deposition conditions, TEM and HRTEM examinations indicate that the deposited nanostructures are bamboo-like multiwalled carbon nanotubes (MWNTs) with a wall thickness of 2030 graphene layers. Electrical conductivity of the as-deposited MWNTs can be greatly improved by subjecting to 760 °C heat treatment under nitrogen atmosphere. The results demonstrate that the amounts of CNTs and bridges are tunable with the Ni catalyst plating time. Under the present experimental configuration and at a catalyst plating time of 20 s, countable numbers of bridges can be obtained, which are selectively and horizontally grown on the areas of the pattern with Ni catalyst. This process can be a step approaching the application of CNTs in electronic devices.     

Effect of Addition of Ni metal catalyst onto the Co and Fe supported catalysts for the formation of carbon nanotubes

Production of novel porous material is a major target in current material science research due to its wide applications. As carbon nanotube (CNTs) is a one dimensional hollow structure it is also one of the promising materials in applications ranging from electronics to hydrogen storage medium. Catalytic chemical vapor deposition (CCVD) is a method whereby CNTs can be produced in large amount. Thus, in this work, we have synthesized CNTs via pyrolysis of acetylene using various supported transition-metal catalysts in a fixed-bed reactor. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to investigate the CNTs structure. The structures of nanotubes formed by acetylene pyrolysis were dependent on the catalysts used. It was found that alumina supported Ni/Fe catalyst inhibited the formation of CNTs growth while alumina supported Ni/Co catalyst gave high density of CNTs. However, nanotubes grown over alumina supported Ni/Fe catalyst were less dense due to the deactivation of the catalyst at the early stage of the pyrolysis process.     

Effect of Addition of Ni metal catalyst onto the Co and Fe supported catalysts for the formation of carbon nanotubes

Production of novel porous material is a major target in current material science research due to its wide applications. As carbon nanotube (CNTs) is a one dimensional hollow structure it is also one of the promising materials in applications ranging from electronics to hydrogen storage medium. Catalytic chemical vapor deposition (CCVD) is a method whereby CNTs can be produced in large amount. Thus, in this work, we have synthesized CNTs via pyrolysis of acetylene using various supported transition-metal catalysts in a fixed-bed reactor. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to investigate the CNTs structure. The structures of nanotubes formed by acetylene pyrolysis were dependent on the catalysts used. It was found that alumina supported Ni/Fe catalyst inhibited the formation of CNTs growth while alumina supported Ni/Co catalyst gave high density of CNTs. However, nanotubes grown over alumina supported Ni/Fe catalyst were less dense due to the deactivation of the catalyst at the early stage of the pyrolysis process.     

Controlling the diameter distribution of carbon nanotubes grown from camphor on a zeolite support

Single-wall and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively) of controlled diameter distribution were selectively grown by thermal decomposition of a botanical hydrocarbon, camphor, on a high-silica zeolite support impregnated with Fe-Co catalyst. Effects of catalyst concentration, growth temperature and camphor vapor pressure were investigated in wide ranges, and diameter distribution statistics of as-grown nanotubes was analyzed. High yields of metal-free MWNTs of fairly uniform diameter (∼10 nm) were grown at 600-700 °C, whereas significant amounts (∼30%) of SWNTs were formed at 850-900 °C within a narrow diameter range of 0.86-1.23 nm. Transmission electron microscopy and micro-Raman spectroscopy reveal that camphor-grown nanotubes are highly graphitized as compared to those grown from conventional CNT precursors used in chemical vapor deposition.     

H2S oxidation by multi-wall carbon nanotubes decorated with tungsten sulfide

Tungsten sulfide catalysts decorated on single and multiwall carbon nanotubes (SWNTs & MWNTs) and activated carbon were synthesized, and XRD, ICP, SEM, TEM and ASAP analyses were employed to acquire the characteristics of each catalyst. Afterwards a gas flow containing 5,000 ppm of H₂S was passed over the catalyst in gas hour space velocity (GHSV) of 5,000 h^?1, temperature of 65 °C, steam volume percent of 20 and O₂/H₂S ratio equal to 2. The results revealed that the catalyst supported on MWNTs exhibited higher conversion amongst its counterparts. Then effects of GHSV, steam volume percent in the feed, catalyst loading and temperature were investigated on conversion of hydrogen sulfide to elemental sulfur for tungsten sulfide catalyst decorated on MWNTs.     

Preferential Growth of Semiconducting Single-Walled Carbon Nanotubes on Substrate by Europium Oxide

In this paper, we have demonstrated that europium oxide (Eu₂O₃) is a new type of active catalyst for single-walled carbon nanotubes (SWNTs) growth under suitable conditions. Both random SWNT networks and horizontally aligned SWNT arrays are efficiently grown on silicon wafers. The density of the SWNT arrays can be altered by the CVD conditions. This result further provides the experimental evidence that the efficient catalyst for SWNT growth is more size dependent than the catalysts themselves. Furthermore, the SWNTs from europium sesquioxides have compatibly higher quality than that from Fe/Mo catalyst. More importantly, over 80% of the nanotubes from Eu₂O₃ are semiconducting SWNTs (s-SWNTs), indicating the preferential growth of s-SWNTs from Eu₂O₃. This new finding could open a way for selective growth of s-SWNTs, which can be used as high-current nanoFETs and sensors. Moreover, the successful growth of SWNTs by Eu₂O₃ catalyst provides new experimental information for understanding the preferential growth of s-SWNTs from Eu₂O₃, which may be helpful for their controllable synthesis.     

Production of Carbon Nanotube by Ethylene Decomposition over Silica-Coated Metal Catalysts

Formation of carbon nanofibers (CNFs) and carbon nanotubes (CNTs) through the decomposition of ethylene at 973 K was achieved using various metal catalysts covered with silica layers. CNFs of various diameters were formed by ethylene decomposition over a Co metal catalyst supported on the outer surface of the silica. In contrast, silica-coated Co catalysts formed CNTs with uniform diameters by ethylene decomposition. Silica-coated Ni/SiO₂ and Pt/carbon black also formed CNTs with uniform diameters, while CNFs and CNTs with various diameters were formed over Ni/SiO₂ and Pt/carbon black without a silica coating. These results indicate that silica layers that envelop metal particles prevent sintering of the metal particles during ethylene decomposition. This results in the preferential formation of CNTs with a uniform diameter.     

Low cost growth route for single-walled carbon nanotubes from decomposition of acetylene over magnesia supported Fe-Mo catalyst

A large amount of single wall carbon nanotubes (SWNTs) was successfully produced by thermal decomposition of C₂H, at 800 °C over magnesia supported Fe-Mo bimetallic catalysts in a tubular flow reactor under an atmosphere of hydrogen flow. The growth density of SWNTs increased with increasing the weight percent of the catalyst metals (wt% ratio of two metals: 50 : 50) supported on magnesia (MgO) from 5 to 30 wt%. The yield of SWNTs reached 144.3% over 30 wt% metal-loaded catalyst. Raman measurements showed the growth of bundle type SWNTs with diameters ranging from 0.81 to 1.96 nm. The growth of SWNTs was also identified by thermal gravimetric analysis (TGA) and Raman spectroscopy.     

Carbon nanotubes/SiC whiskers composite prepared by CVD method

Selective growth of carbon nanotubes (CNTs) on silicon carbide (SiC) substrate will create some new applications in composites and electronic devices by combining their mechanical and physical properties. Multi-walled CNTs were successfully grown on SiC whiskers using a conventional xylene–ferrocene chemical vapor deposition process. A thin oxide layer was created on the surface of the SiC whiskers by high-temperature annealing in air before CNT growth. The effect of catalyst morphology and chemistry on the growth of CNTs was analyzed. Our technique may be further applied to the controlled growth of CNTs on any other SiC substrates.     

Large-scale synthesis of n-type gallium nitride nanowires using NiI2-decorated carbon nanotubes as a reactant

This study demonstrates the first example of the use of NiI₂-filled carbon nanotubes (CNTs) for the synthesis of GaN nanowires (NWs). Large quantities of single crystal and n-type GaN NWs were synthesized after NiI₂-decorated CNTs reacted with Ga₂O₃ in NH₃. Comparatively few short GaN NWs (<1 μm) were synthesized in the absence of CNTs, and GaN NWs were found to be synthesized with a reasonable yield using graphite as a reactant. Therefore, CNTs play no role as a template in the growth of NW, but this growth is assisted by NiI₂ nanocrystals via a vapour-liquid-solid mechanism in which the presence of carbon materials facilitates the reduction of Ga₂O₃ to Ga₂O and Ga, thus providing a constant Ga source during the growth of the NW. Furthermore, the use of NiI₂-filled single wall carbon nanotubes results in a higher NW yield at a low growth temperature (600 °C), indicating that NiI₂-filled single wall CNTs can serve as an effective reactant for the synthesis of GaN NWs.     

Preparation of sea urchin-like carbons by growing one-dimensional nanocarbon on mesoporous carbons

One-dimensional nanocarbons, including carbon nanotubes and nanowires, were grown on catalyst-seeded mesoporous carbons using thermal chemical vapor deposition. The catalyst was applied to the mesoporous carbons by a dip coating process followed by a high temperature reduction. The growth of carbon nanotubes/nanowires then took place through the thermal decomposition of methane at temperatures of 800 °C or 900 °C. Carbon nanotubes/nanowires grown on mesoporous carbon particles provide interconnects among the particles. Intimate contacts between the CNTs/CNWs and the mesoporous carbons were also observed. Due to these interconnects and the intimate contacts, the electrical resistance mesoporous carbons having carbon nanotubes/nanowires is approximately 30% lower than that of mesoporous carbons.