Synthesis of bamboo-like carbon nanotubes on a copper foil by catalytic chemical vapor deposition from ethanol

Bamboo-like carbon nanotubes (CNTs) were synthesized on a copper foil by catalytic chemical vapor deposition (CVD) from ethanol. The effects of temperature (700–1000 °C) and duration (5–60 min) on the growth of CNTs were investigated. Morphology and structure of the CNTs were characterized by scanning and transmission electron microscopy and Raman spectroscopy. The yield and size of the CNTs increased with temperature. Those prepared at 700 °C had a copper droplet tip and those at 800–900 °C had a copper nanoparticle inside. An amorphous carbon film consisted of a porous and non-porous layer was observed on the surface of the copper substrate, and the CNTs were really grown from this carbon film. The thickness of the carbon film increased from 187 to 900 nm when the duration increased from 5 to 60 min. It was also found that the copper foil became porous after ethanol CVD treatment. The growth mechanism of the CNTs, carbon film and motion of copper catalyst were discussed. It is proposed that a carbon film first deposited on the top surface of the copper foil while the top surface of the copper foil partially melted and migrated across the carbon film, where CNTs formed.     

CVD growth and field electron emission of aligned carbon nanotubes on oxidized Inconel plates without addition of catalyst

Direct growth of carbon nanotubes (CNTs) on Inconel 600 sheets was investigated using plasma enhanced hot filament chemical vapor deposition in a gas mixture of methane and hydrogen. The Inconel 600 sheets were oxidized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) before CNT deposition. The structure and surface morphology of the pre-treated substrate sheets and the deposited CNTs were studied by scanning electron microscopy (SEM) and X-ray diffraction. The field electron emission (FEE) properties of the CNTs were also tested. The SEM results show that well aligned CNTs have been grown on the pre-treated Inconel sheets without addition of any catalysts and the higher treatment temperature resulted in CNTs with better uniformity, indicating that the oxidation pre-treatment of the substrate is effective to enhance the CNT growth. FEE testing shows that CNTs with better height uniformity exhibit better FEE characteristics.     

Liquid-phase transfer hydrogenation of furfural to furfuryl alcohol on Cu–Mg–Al catalysts

The liquid-phase transfer hydrogenation of furfural on Cu-based catalysts was studied. Catalysts were prepared by incipient wetness impregnation (Cu/SiO₂) and co-precipitation (Cu–Mg–Al). The effect of metal-support interaction, hydrogen donor, copper loading and temperature on catalytic performance was evaluated. Small particles, strongly interacting with a spinel-like matrix, had higher capability for transferring hydrogen than large ones having low interaction with support. An important increase in reaction rate was observed when temperature was raised from 110 to 150 °C. Thus, it was possible to attain complete furfural conversion to furfuryl alcohol with Cu(40%)–Mg–Al after 6 h at 150 °C.     

Self-organization of nitrogen-doped carbon nanotubes into double-helix structures

Self-organization of nitrogen-doped carbon nanotube (N-CNT) double helices was achieved by chemical vapor deposition (CVD) with Fe–Mg–Al layered double hydroxides (LDHs) as the catalyst precursor. The as-obtained N-CNT double helix exhibited a closely packed nanostructure with a catalyst flake on the tip, which connected the two CNT strands on both sides of the flake. A mechanism for the self-organization of N-CNTs into double-helix structures with a moving catalyst head is proposed. Effective carbon/nitrogen sources, high-density active catalyst nanoparticles, space confinement, and the precise chiral match between the two CNT strands are found to be crucial for the N-CNT double helix formation. The morphologies of N-CNTs can be well tuned between bamboo-like and cup-stacked structures, and a CNT/N-CNT heterojunction can be constructed by changing the carbon feedstock from C₂H₄ to CH₃CN during CVD growth. N-CNT double helices with a length of 10–36 μm, a screw pitch of 1–2 μm, a CNT diameter of 6–10 nm, and a N-content of 2.59 at.% can be synthesized on the LDH catalysts by the efficient CVD growth.     

Effect of the dimensions of carbon nanotube channels on copper–cobalt–cerium catalysts for higher alcohols synthesis

A series of carbon nanotube (CNT)-supported copper–cobalt–cerium catalysts were prepared and investigated for higher alcohols synthesis. The superior selectivity for the formation of ethanol and C_2 + alcohols achieved using the CuCoCe/CNT(8) catalyst was 39.0% and 67.9%, respectively. The diameters of CNTs considerably influence the distribution of metal particles and the electronic interaction between the tube surface and the active species. The electronic effect between the encapsulated Co species and the inner surface is greatly improved in the narrowest CNT channel, which is expected to facilitate the reduction of cobaltous oxide and promote the alcohols yield remarkably (291.9 mg/g_cath).     

Carbon nanotube and nanofiber syntheses by the decomposition of methane on group 8–10 metal-loaded MgO catalysts

We have found that several precious metal-loaded MgO catalysts are active in the formation of carbon nanotube (CNT) by the chemical vapor deposition (CVD) of methane. The catalysts were prepared with nine metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt) by impregnation onto a high surface area MgO. CNT synthesis was carried out in the temperature range from 600 °C to 1000 °C after reduction with H₂ at 800 °C.The amount of carbon deposited and crystallinity in the produced CNT on nine metals showed interesting tendencies: (i) The amount of carbon formed increased in the following transition series metals: first < second < third row transition elements, and (ii) the index of crystallinity I_G/I_D in Raman-bands of the CNTs decreased in the following order: 8 > 9 > 10 in the Periodic Table. Group 8 and 9 metals produced tube type fibers composed of the graphite layers arranged parallel to the fiber axis. On the other hand, carbon nanofibers (CNFs) grown on group 10 metals had herringbone type graphene sheets.     

Single stage production of carbon nanotubes using microwave technology

Carbon nanotubes (CNTs) were produced by gas phase single stage tubular microwave chemical vapor deposition (TM–CVD) using ferrocene as a catalyst and acetylene (C₂H₂) and hydrogen (H₂) as precursor gasses. The effect of the process parameters such as microwave power, radiation time, and gas ratio of C₂H₂/H₂ was investigated. The CNTs were characterized using scanning and transmission electron microscopy (TEM), and by thermogravimetric analysis (TGA). Results reveal that the optimized conditions for CNT production were 900 W reaction power, 35 min radiation time, and 0.6 gas ratio of C₂H₂/H₂. TEM analyses revealed that the uniformly dispersed vertical alignment of multiwall carbon nanotubes (MWCNTs) have diameters ranging from 16 to 23 nm. The TGA analysis showed that the purity of CNT produced was 98%.     

Alcohol-assisted rapid growth of vertically aligned carbon nanotube arrays

Millimeter-to-centimeter scale vertically aligned carbon nanotube (VACNT) arrays are widely studied because of their immense potential in a range of applications. Catalyst control during chemical vapor deposition (CVD) is key to maintain the sustained growth of VACNT arrays. Herein, we achieved ultrafast growth of VACNT arrays using Fe/Al₂O₃ catalysts by ethanol-assisted two-zone CVD. One zone was set at temperatures above 850 °C to pyrolyze the carbon source and the other zone was set at 760 °C for VACNT deposition. By tuning synthesis parameters, up to 7 mm long VACNT arrays could be grown within 45 min, with a maximal growth rate of ∼280 μm/min. Our study indicates that the introduction of alcohol vapor and separation of growth zones from the carbon decomposition zone help reduce catalyst particle deactivation and accelerate the carbon source pyrolysis, leading to the promotion of VACNT array growth. We also observed that the catalyst film thickness did not significantly affect the CNT growth rate and microstructures under the conditions of our study. Additionally, the ultralong CNTs showed better processability with less structural deformation when exposed to solvent and polymer solutions. Our results demonstrate significant progress towards commercial production and application of VACNT arrays.     

Effect of particle size,heating rate and CNT addition on densification,microstructure and mechanical properties of B4C ceramics

Monolithic B₄C ceramics and B₄C–CNT composites were prepared by spark plasma sintering (SPS). The influence of particle size, heating rate, and CNT addition on sintering behavior, microstructure and mechanical properties were studied. Two different B₄C powders were used to examine the effect of particle size. The effect of heating rate on monolithic B₄C was investigated by applying three different heating rates (75, 150 and 225 °C/min). Moreover, in order to evaluate the effect of CNT addition, B₄C–CNT (0.5–3 mass%) composites were also produced. Fully dense monolithic B₄C ceramics were obtained by using heating rate of 75 °C/min. Vickers hardness value increased with increasing CNT content, and B₄C–CNT composite with 3 mass% CNTs had the highest hardness value of 32.8 GPa. Addition of CNTs and increase in heating rate had a positive effect on the fracture toughness and the highest fracture toughness value, 5.9 MPa m^1/2, was achieved in composite with 3 mass% CNTs.     

Low temperature growth of carbon nanotubes on Si substrates in high vacuum

Carbon nanotube (CNT) growth was carried out on SiO₂/Si substrates using an alcohol gas source in a high vacuum without any carbon decomposition processes. In the Raman spectra of the grown CNTs, both the G/Si peak intensity ratio and G/D peak intensity ratio indicated that the optimum growth temperature became lower as the pressure decreased. By reducing the pressure to 1 × 10^− 4 Pa, CNTs could be grown at 400 °C, and the G/D ratio was about 16, indicating that the quality of the grown CNTs was good, taking into account the low growth pressure. In addition, the Raman spectra in the radial breathing mode (RBM) region showed that the diameter distribution of the grown CNTs was dependent on both the growth pressure and temperature, and the relative intensity of the RBM peaks from small-diameter CNTs increased as the growth pressure and/or temperature was reduced.     

Thermogravimetric study on pyrolysis of biomass with Cu/Al2O3 catalysts

The Cu/Al₂O₃ catalysts of three different compositions (10, 20 and 30 wt.% Cu loading), have been investigated with regard to their catalytic effects on pyrolysis of paper biomass species (up to 800 °C) by thermogravimetric analysis (TGA) experiments. The results show that catalysts made devolatilization at lower (below 200 °C) and middle temperature (200–400 °C) regions in the pyrolysis of the biomass species, and the temperature reduction effects follow the order: 30 > 20 > 10 wt.% copper loading. Although the catalysts with 10 and 20 wt.% copper have shown almost similar activity, whereas dehydration reaction was enhanced almost 40% in the presence of 30 wt.% copper-loaded catalyst. At the same time, the amount of residue at the end of the reaction also decreased with increase in the copper loading from 10 to 30 wt.%. At higher temperatures (above 400 °C), the catalyst with greater copper loaded worked more nicely possibly due to the enhancement of the depolymerization reaction over dehydration of cellulose in presence of more basic catalysts. The catalysts were characterized by using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area analysis and scanning electron microscopy (SEM). XRD results show the formation of CuAl₂O₄ spinel and Cu₂O phase in the catalysts.     

Improved thermal interface property of carbon nanotube–Cu composite based on supercritical fluid deposition

In this paper, we present a new synthesis method of carbon nanotubes (CNTs)-copper (Cu) composite on a silicon substrate using combination of supercritical fluid deposition (SCFD) and electrochemical plating (ECP) process. Deposition of a Cu layer onto CNTs is carried out under supercritical condition, and the CNTs–Cu composite with high-density Cu is synthesized by additional ECP process. The Cu layer deposited by SCFD functions as a seed layer for ECP, and spaces between neighboring CNTs are filled by Cu. The measured density of the CNTs–Cu composite is 8.2 ± 0.3 g/cm³, and the volume percentage of voids is 3–6%. The evaluated thermal resistance including the thermal interface resistance and bulk resistance of the composite is as low as 28.4 mm² K W⁻¹ at a contact pressure of 0.2 MPa. A CNT brush formed on the composite surface can reduce the thermal resistance to be 68.4 mm² K W⁻¹ at a contact pressure of 0.25 MPa. The CNTs–Cu composite shows the ability applicable to many microelectronics applications as a thermal interface material.     

Synthesis,microstructure and electrical conductivity of carbon nanotube–alumina nanocomposites

Carbon nanotube–alumina (CNT–Al₂O₃) nanocomposites have been synthesized by direct growth of carbon nanotubes on alumina by chemical vapor deposition (CVD) and the as-grown nanocomposites were densified by spark plasma sintering (SPS). Surface morphology analysis shows that the CNTs and CNT bundles are very well distributed between the matrix grains creating a web of CNTs as a consequence of their in situ synthesis. Even after the SPS treatment, the CNTs in the composite material are still intact. Experimental result shows that the electrical conductivity of the composites increases with the CNT content and falls in the range of the conductivity of semiconductors. The nanocomposite with highest CNT content has electrical conductivity of 3336 S/m at near room temperature, which is about 13 orders of magnitude increase over that of pure alumina.     

Experiments on C nanotubes synthesis by Fe-assisted ethane decomposition

We performed experiments on the synthesis of carbon nanotubes (CNTs) by iron-catalyzed chemical vapor deposition (CVD) in C₂H₆ + H₂ atmosphere. We varied flow-rates of reactant gases (ethane: 30–120 sccm, hydrogen: 0–120 sccm), as well as their ratio, in order to study the evolution of the growth kinetics. We used scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy to investigate the morphologies, dimensions and crystalline structure of the samples. Our results demonstrate the crucial role played by H₂ in the enhancement of C diffusion-rate and in the consequent development of ordered and smooth graphene layers. A faster growth-rate is achieved by the increase of C₂H₆ flow-rate. However, if H₂ flow-rate is not adequately enhanced, the improvement is only apparent. The excess of C supplied gives rise to deposition of amorphous carbon onto the CNT walls, and to the co-production of different nanostructures. A substantial agreement is found with results reported for CVD growth of CNTs by the use of different catalysts, reactants and gas-flowing setups.     

Visible light-driven mesoporous Au–TiO2/SiO2 photocatalysts for advanced oxidation process

Au–TiO₂/SiO₂ heterogeneous catalysts with different Au contents were successfully synthesized by a facile hydrothermal process and their photocatalytic activity towards reduction of Rose Bengal (RB), Methyl Blue (MB), Rhodamine B (RhB) and Congo Red (CR) was investigated in the presence of sodium borohydride (NaBH₄) for advanced oxidation process (AOP). The results reveal that 3 wt% Au loaded in TiO₂/SiO₂ can significantly degrade high RB concentration dye (>95%, 0.3 g/L, 12 pH) within 20 min of irradiation time. All catalysis reaction followed the pseudo-first order rate reaction with high correlation coefficient. The effect of loading of Au nanoparticles (1–5 wt%) along with variation in dye concentration (100–500 ppm), pH of solution (2–12), catalysts dosage (0.1–0.5 g/L), and reaction temperature (30–80 °C) were also studied. The present works shows the superior performance of Au–TiO₂/SiO₂ heterogeneous catalysts to be related to the high dispersion of Au nanoparticles in the TiO₂/SiO₂ and to the catalytic effect between gold and TiO₂.     

Pressureless sintering of carbon nanotube–Al2O3 composites

Alumina ceramics reinforced with 1, 3, or 5 vol.% multi-walled carbon nanotubes (CNTs) were densified by pressureless sintering. Commercial CNTs were purified by acid treatment and then dispersed in water at pH 12. The dispersed CNTs were mixed with Al₂O₃ powder, which was also dispersed in water at pH 12. The mixture was freeze dried to prevent segregation by differential sedimentation during solvent evaporation. Cylindrical pellets were formed by uniaxial pressing and then densified by heating in flowing argon. The resulting pellets had relative densities as high as ～99% after sintering at 1500 °C for 2 h. Higher temperatures or longer times resulted in lower densities and weight loss due to degradation of the CNTs by reaction with the Al₂O₃. A CNT/Al₂O₃ composite containing 1 vol.% CNT had a higher flexure strength (～540 MPa) than pure Al₂O₃ densified under similar conditions (～400 MPa). Improved fracture toughness of CNT–Al₂O₃ composites was attributed to CNT pullout. This study has shown, for the first time, that CNT/Al₂O₃ composites can be densified by pressureless sintering without damage to the CNTs.     

Highly dispersed Mn–Ce mixed oxides supported on carbon nanotubes for low-temperature NO reduction with NH3

A series of Mn–Ce mixed-oxide catalysts supported on carbon nanotubes (CNTs) were prepared for the first time and used for the selective catalytic reduction of NO with NH₃. Mn(0.4)-Ce/CNTs catalysts with loading from 0.6% to 1.8% (molar ratio) in our tests showed more than 90% NO conversion at 120–180 °C at a high space velocity of 42,000 h^− 1. Transmission electron microscopy confirmed that the particle size of Mn–Ce mixed oxides supported on CNTs was 2 to 4 nm. BET result indicated Mn–Ce mixed-oxide catalysts obtained enlarged surface area and pore volume which was beneficial to the catalytic activity.     

RF-PECVD growth and nitrogen plasma functionalization of CNTs on copper foil for electrochemical applications

This work describes an efficient way to improve the adhesion, growth rate and density of CNTs on copper substrate using radio-frequency plasma enhanced chemical vapor deposition (RF-PECVD). The adhesion of an alumina buffer layer to the copper substrate is critical for the successful growth of CNTs. Hydrogen plasma was performed on the copper substrate to reduce copper oxide from the surface. The effect of two intermediate layers (Ti, Ni), as individual or in combination, between alumina and copper substrate on the CNT growth has been investigated. Furthermore, a nitrogen plasma treatment was carried out to functionalize the obtained CNTs. Electrochemical measurements were performed using CNTs grown on a copper substrate as electrodes and LiClO₄ as electrolyte. The specific capacitance of the obtained electrodes increases from 49 up to 227 Fg^− 1 for untreated and nitrogen-plasma treated CNTs at a scan rate of 10 mVs^− 1, respectively.     

Low temperature growth mechanisms of vertically aligned carbon nanofibers and nanotubes by radio frequency-plasma enhanced chemical vapor deposition

Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most widely used thermal CVD method, in which the synthesis temperature was 400–850 °C, RF-PECVD had a huge advantage in low temperature growth and control of other deposition parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature growth mechanisms are not clearly understood. Here, low temperature growth mechanisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemistry, catalyst, substrate characteristics, temperature, and type of gas.     

Novel straight synthesis of super-microporous Cu/Al2O3 catalyst with high CH4-SCR-NO activity

A super-microporous nanocrystalline 15 mol% copper–alumina (pore size 1 to 2 nm) was prepared via a facile one-pot evaporation-induced self-assembly (EISA) strategy with an economic template. After removing the template at 500 °C, the sample exhibited high specific surface area (larger than 580 m²/g), narrow pore size distribution and high thermal stability. Owing to its large surface area and the good dispersion of active Cu centers, the sample exhibited an enhanced catalytic activity in the selective catalytic reduction (SCR) of NO with methane than those of conventional Cu/Al₂O₃ catalysts. Additionally, it presented remarkable activity in direct NO decomposition.