Selective growth of single-walled carbon nanotubes over Co–MgO catalyst by chemical vapor deposition of methane

The selective synthesis of SWCNTs with narrow chirality and diameter distribution by methane decomposition over a Co–MgO catalyst is reported. Raman spectroscopy, temperature programmed oxidation (TPO), UV–Vis–NIR absorption spectroscopy, and nitrogen physisorption were used to probe SWCNTs morphology, reaction selectivity, SWCNTs chirality and diameter distribution, and carbon yield. The catalyst was examined by nitrogen physisorption, X-ray diffraction (XRD), temperature programmed reduction (TPR), and UV–Vis-diffuse reflectance spectroscopy to elucidate the structure and chemical state of the species responsible for SWCNT growth. The results established a clear link between the degree of dispersion of Co species inside the MgO lattice and the catalyst activity and selectivity for SWCNT growth. High dispersion and stabilization of Co species influenced catalytic activity for methane decomposition and the high SWCNT selectivity. The yield of carbon and SWCNT selectivity increased with an increase in temperature, however, SWCNTs diameter distribution shifts to larger diameter tubes as synthesis temperature was increased.     

Prospective growth region for chemical vapor deposition synthesis of carbon nanotube on C–H–O ternary diagram

Chemical vapor deposition has become a standard process for synthesizing carbon nanotubes. Since the successful use of chemical vapor deposition for the first time, much effort has been expended into exploring various carbon sources that can be used to synthesize carbon nanotubes, such as methane, ethane, and ethanol. However, whole perspectives for suitable carbon sources have not been clear. In this study, we performed experiments in order to determine that the appropriate C–H–O components ratio in raw materials can be used to synthesize carbon nanotubes. We also examined a variety of raw materials in our newly developed round-trip-type vacuum furnace in order to determine whether they could be used to synthesize a carbon nanotube. We used Raman spectroscopy to identify the developed carbon nanotube, and we plotted the component ratios of effective and ineffective materials on a C–H–O ternary diagram; in this diagram, the growth region became highly apparent. It should be noted that for the growth of the carbon nanotube, this region should satisfy the equation O < C < (H + O) in molar ratio. Furthermore, it was observed that adjusting the component ratios by mixing raw materials did not cause an inconsistency in the growth region.     

Synthesis of single-walled carbon nanotubes over a spin-coated Fe catalyst in an ethanol–PEG colloidal solution

Single-walled carbon nanotubes (SWCNTs) have been grown on flat silicon oxide substrates by the decomposition of methane. The spin-coated iron(III) nitrate with a concentration of 40 mmol/L diluted in a colloidal solution with ratio 1:1 (v/v) of absolute ethanol to PEG-400 was found to form iron nanoparticles that are small enough to grow SWCNTs. The role of PEG was to interact with iron ions and encapsulate the iron, thus preventing agglomeration, while the absolute ethanol isolated the PEG–iron micelles. The ratio of absolute ethanol to PEG controlled the viscosity and the distance between PEG–encapsulated iron micelles, and subsequently governed the size and density of the iron nanoparticles formed. To reduce the effect of surface tension that will disturb the uniformity of a thin colloid film, –OH groups were introduced on the silicon wafer by a piranha solution and the hydrogen bonds formed with PEG preserved the uniformity of the iron nanoparticle distribution during the synthesis of SWCNTs.     

Fabrication of core-shell structured TiC–Fe composite powders by fluidized bed chemical vapor deposition

Fluidized bed chemical vapor deposition (FBCVD) was an effective way of preparing the core-shell structured TiC–Fe composite powders by employing FeCl₃ as a precursor. Fully covered TiC–Fe composite powders with the controllable Fe contents were readily achievable. An excellent interfacial bonding was formed between the TiC and the deposited Fe coating. The defluidization caused by the directional growth and self-nucleation-aggregation of the deposited Fe particles was the major barrier to depositing high-Fe-content composite powders. But it could be prevented by controlling the gas partial pressure of precursor and further eliminating the directional growth mode and self-nucleation behavior of Fe atoms. The optimal deposition temperature was 600°C and the partial pressure was about 20 kPa, corresponding to the gasification temperature of 275°C.     

Growth of carbon nanotubes on the surface of carbon fiber using Fe–Ni bimetallic catalyst at low temperature

This article provides a method for growing carbon nanotubes(CNTs) on carbon fibers(CFs) using iron and nickel as catalysts at low temperatures. This series of experiments was conducted in a vacuum chemical vapor deposition(CVD)furnace. It is found that Fe–Ni catalysts, which have a certain thickness and can be better combined with resins when manufacturing composite materials, are more ideal for the growth of CNTs than single metal catalysts. At the same time, it is proved that the CVD process worked best at 450 °C. The mechanical property test proved the reinforcing effect of CNTs on carbon fiber, the single-filament tensile strength of CFs obtained by using Fe–Ni catalyst at 450 °C was 11% higher than that of Desized CFs. The bonding strength of carbon fiber and resin has also been significantly improved. When synthesized at low temperature, CNTs exhibited a hollow multi-wall structure.     

Synthesis of multiwalled carbon nanotubes supported on M/MCM-41 (M = Ni,Co and Fe) mesoporous catalyst by chemical vapour deposition method

Aim of this research is to develop an effective way in producing multi-walled carbon nanotubes (MWNTs) via chemical vapour deposition method using acetylene as carbon source and synthesized mesoporous M/MCM-41 (M?=?Ni, Co and Fe) as catalyst. The mesoporous MCM41 is synthesized by using sodium metasilicate as silica source of frameworks and cetyltrimethylammonium bromide as template. The effect of temperatures and growth times are investigated to produce MWNTs with high yield and high quality. The low-angle X-ray diffraction (XRD), Fourier transform infrared spectroscopy and scanning electron microscopy results verified the formation of MCM41. Meanwhile, high-angle XRD, Raman spectra and transmission electron microscopy results confirmed the synthesized carbon nanotubes at 600?°C and growth time for 30 min are multi-walled. The yield obtained is 1353 mg in 30 min. It shows that the MCM-41 has a promising potential to produce MWNTs at low cost and shorter duration.     

Dry reforming of methane over palladium–platinum on carbon nanotube catalyst

A dry reforming (DR) catalyst based on bimetallic Pd–Pt supported on carbon nanotubes is presented. The catalyst was prepared using a microwave-induced synthesis. It showed enhanced DR activity in the 773–923?K temperature range at 3 atm. Observed carbon balances between the reactant and product gases imply minimal carbon deposition. A global three-reaction (reversible) kinetic model—consisting of DR, reverse water gas shift, and CH₄ decomposition (MD)—adequately simulates the observed concentrations, product H₂/CO ratios, and reactant conversions. Analysis shows that, under the conditions of this study, the DR and MD reactions are net forward and far from equilibrium, while the RWGS is near equilibrium.     

Cobalt supported on carbon nanotubes — A promising novel Fischer–Tropsch synthesis catalyst

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNT) supported and γ–alumina-supported cobalt catalysts with different amounts of cobalt are reported. Up to 40 wt.% of cobalt is added to the supports by the impregnation method. The effect of the support on the reducibility of the cobalt oxide species, dispersion of the cobalt, average cobalt clusters size, water–gas shift (WGS) activity and activity and selectivity of FTS is investigated. Using carbon nanotubes as cobalt catalyst support was found to cause the reduction temperature of cobalt oxide species to shift to lower temperatures. The strong metal-support interactions are reduced to a large extent and the reducibility of the catalysts improved significantly. CNT aided in well dispersion of metal clusters and average cobalt clusters size decreased. Results are presented showing that the hydrocarbon yield obtained by inventive CNT supported cobalt catalyst is surprisingly much larger than that obtained from cobalt on alumina supports. The maximum concentration of active surface Co° sites and FTS activity for alumina and CNT supported catalysts are achieved at 34 wt.% and 40 wt.% cobalt loading respectively. CNT caused a slight decrease in the FTS product distribution to lower molecular weight hydrocarbons.     

Local “repristinization” of oxidized single-walled carbon nanotubes by laser treatment

Though having passed the second decade since their discovery, carbon nanotubes (CNTs) still hold promise in different fields, and many steps forward have been done. However, one major limit is given by their lack of solubility, which still represents a challenge, given the need to properly handle the material for many applications. The most efficient strategies to solve this problem often rely on a covalent chemical modification of CNT structure, in order to prevent inter-tube interactions. However, many applications, being based on CNT peculiar electronic properties, require structural integrity, and they are therefore incompatible with such strategies.We prepared strongly oxidized single-walled carbon nanotubes, with a dramatically improved dispersibility, and we performed a subsequent localized repristinization by means of laser-induced heating of the sample, during Raman analysis, consisting in both removal of the amorphous material and healing of structural defects. Our finding highlights an effect which all researchers in the field must be aware of, when using Raman spectroscopy for characterization purposes. Moreover, this local laser effect was systematically investigated in order to gain a deeper understanding of the phenomenon.     

Fischer–Tropsch synthesis on mono- and bimetallic Co and Fe catalysts supported on carbon nanotubes

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNTs)-supported bimetallic cobalt/iron catalysts is reported. Up to 4 wt.% of iron is added to the 10 wt.% Co/CNT catalyst by co-impregnation. The physico-chemical properties, FTS activity and selectivity of the bimetallic catalysts were analyzed and compared with those of 10 wt.% monometallic cobalt and iron catalysts at similar operating conditions (H₂/CO = 2:1 molar ratio, P = 2 MPa and T = 220 °C). The metal particles were distributed inside the tubes and the rest on the outer surface of the CNTs. For iron loadings higher than 2 wt.%, Co–Fe alloy was revealed by X-ray diffraction (XRD) techniques. 0.5 wt.% of Fe enhanced the reducibility and dispersion of the cobalt catalyst by 19 and 32.8%, respectively. Among the catalysts studied, cobalt catalyst with 0.5% Fe showed the highest FTS reaction rate and percentage CO conversion. The monometallic iron catalyst showed the minimum FTS and maximum water–gas shift (WGS) rates. The monometallic cobalt catalyst exhibited high selectivity (85.1%) toward C₅+ liquid hydrocarbons, while addition of small amounts of iron did not significantly change the product selectivity. Monometallic iron catalyst showed the lowest selectivity for 46.7% to C₅+ hydrocarbons. The olefin to paraffin ratio in the FTS products increased with the addition of iron, and monometallic iron catalyst exhibited maximum olefin to paraffin ratio of 1.95. The bimetallic Co–Fe/CNT catalysts proved to be attractive in terms of alcohol formation. The introduction of 4 wt.% iron in the cobalt catalyst increased the alcohol selectivity from 2.3 to 26.3%. The Co–Fe alloys appear to be responsible for the high selectivity toward alcohol formation.     

Diamond growth on WC-Co substrates by hot filament chemical vapor deposition: Effect of filament–substrate separation

Polycrystalline diamond films have been grown by hot filament (HF) chemical vapor deposition on WC-Co bar substrates using different CH₄/H₂ source gas mixing ratios and two different total gas pressures. Each substrate was mounted so as to span a range of HF-substrate separations, d_f, (and thus substrate temperatures) and therefore samples a spread of incident gas phase chemistry and compositions. Spatially resolved scanning electron microscopy and Raman analysis of the deposited material provides a detailed picture of the evolution of film morphology, growth rate, sp³/sp² content and stress with d_f in each deposited sample, and of how these properties vary with process conditions. The experimental study is complemented by two-dimensional model calculations of the HF-activated gas phase chemistry and composition, which succeeds in reproducing the measured growth rates well.     

Comparison of a-C:H films deposited from methane–argon and acetylene–argon mixtures by electron cyclotron resonance–chemical vapor deposition discharges

Hydrogenated amorphous carbon (a-C:H) films are deposited from methane–argon and acetylene–argon gas mixtures in a microwave electron cyclotron resonance plasma reactor. The films deposited with the two different gas mixtures under similar input parameter conditions have substantially different properties, including deposition rate, mass density, optical absorption coefficient, refractive index, optical bandgap and hydrogen content. The deposition parameters varied include rf-induced dc substrate bias voltage (0 to −60 V), pressure (1–5 mTorr) and argon/hydrocarbon gas flow ratio (0–1.0). The discharge properties of the two different gas mixtures, including electron temperature, ion saturation current, and residual gas composition of the exit gas flow, are measured to help explain the different deposition results from the two different gas mixtures. The use of lower pressures is found to be critical for obtaining denser, lower hydrogen content films from acetylene. For the methane-deposited films the addition of argon to the discharge increased the film's mass density and lowered the hydrogen content. In both methane- and acetylene-based deposition processes the rf-induced bias is also a critical determining factor of film properties.     

Floating catalyst chemical vapor infiltration of nanofilamentous carbon reinforced carbon/carbon composites – Integrative improvement on the mechanical and thermal properties

Nanofilamentous carbon (NFC) reinforced carbon/carbon composites were produced by floating catalyst chemical vapor infiltration with ferrocene content ranging 0–2.0?wt%. The NFCs and increased graphitization degree led to an improvement on the mechanical and thermal properties. An excellent combination of high strength and thermal conductivity (TC), and low coefficient of thermal expansion (CTE) was reached by adding 0.5–0.8?wt% catalyst. When the content exceeded 0.8wt%, the strength and TC were decreased by the limited NFC growth and matrix transited from rough laminar to isotropic pyrocarbon. After the treatment of 2500?°C, the strength and CTE decreased whereas the TC was increased. With the catalyst contents at 0.5–0.8?wt%, the flexural and shear strength retention ratios achieved a high value of 73.1–74.5 and 79.1–79.4%, respectively, and the in-plane and out-of-plane TCs exhibited maxima of 339.1 and 72.5?W/(m?K). Relatively low CTE was obtained at 2.0?wt% catalyst owing to the increased amount of cracks and pores.     

The structure of 1D and 3D CuI nanocrystals grown within 1.5–2.5 nm single wall carbon nanotubes obtained by catalyzed chemical vapor deposition

Catalyzed chemical vapor deposition (CCVD) grown single wall carbon nanotubes (SWCNT) with diameter of D_m = 1.5–2.5 nm were used as templates to host one-dimensional nanocrystals of CuI. The CuI@SWCNT nanocomposite was obtained using capillary filling of preopened SWCNTs by CuI melt at 650 °C. Nanocomposite structural studies were performed on a FEI Titan 60–300 at 80 kV. According to the model and image simulation CuI crystallizes within 1.5–2.0 nm SWCNTs in the form of one-dimensional crystals with zinc blende or rock salt type unit cell connected by [0 0 1] edges and translated along 〈1 1 0〉. Copper cations occupy tetrahedral or octahedral sites in the lattice. In SWCNTs with D_m > 2.0 nm 3DCuI@SWCNTs were generated. The crystals of copper halides exhibit acceptor behavior as supported by Raman spectroscopy.     

Floating catalyst chemical vapor infiltration of nanofilamentous carbon reinforced carbon/carbon composites – Densification behavior and matrix microstructure

Nanofilamentous carbon (NFC) reinforced carbon/carbon composites were prepared by floating catalyst film boiling chemical vapor infiltration from xylene pyrolysis at 1000–1100 °C using ferrocene as a catalyst. The influence of the catalyst content on the densification behavior and matrix microstructure of the composites was studied. Results showed that the deposition rate of pyrocarbon (PyC) was enhanced remarkably by the catalyst. The density of the composites deposited at a catalyst content of 0–2.0 wt% decreased along both the axial and the negative radial directions. Rough laminar (RL) PyC matrix was formed at 0–0.8 wt% catalyst content by heterogeneous nucleation and growth. A hybrid matrix consisting of RL and isotropic (ISO) PyCs appeared at a catalyst content of 1.2–2.0 wt%. The reasons for this ISO PyC formation were attributed to the deposition of carbon encapsulated iron particles and homogeneous nucleation. A reinforcing network composed of NFCs and vapor grown carbon fibers was formed on the fiber/matrix interface and within the matrix in this floating catalyst process. The structure of NFC transformed from nanotube to nanofiber when the catalyst content was over 0.5 wt%, around which composites of a high density of 1.75 g/cm³ and uniform RL PyC matrix were produced rapidly.     

Benzylacetate synthesis by oxyacetoxylation of toluene on Pd–Bi binary catalyst

Benzylacetate synthesis from toluene, acetic acid and oxygen on Pd–Bi binary catalyst was studied in the liquid phase. By incorporation of Bi with Pd, both the activity and selectivity were improved. Especially better stability was obtained with the catalyst having Pd/Bi = 3. Deactivation of the catalyst was investigated in detail by XRD, XPS, TEM, elemental analysis, EPMA and so on. Comparing the used catalyst with the fresh one, it was indicated that the main cause of deactivation was the dissolution of Pd into the reaction mixture from the most outer surface of the catalyst. By adopting proper reaction conditions to prevent the Pd dissolution, the catalyst having Pd/Bi = 3 was suggested to be used as an industrial catalyst. This revised version was published online in June 2006 with corrections to the Cover Date.     

Preparation of highly oriented β-SiC bulks by halide laser chemical vapor deposition

Highly oriented β-SiC bulks with high hardness were fabricated by halide laser chemical vapor deposition (HLCVD) using SiCl₄, CH₄ and H₂ as precursors. The effects of total pressure (P_tot) and deposition temperature (T_dep) on the preferred orientation, microstructure, deposition rate (R_dep) and micro-hardness were investigated. The 〈110〉-oriented β-SiC bulks were obtained at low P_tot (2–4 kPa), non-oriented β-SiC bulks were obtained at mediate P_tot (6 kPa), and 〈111〉-oriented β-SiC bulks were obtained at high P_tot (10–40 kPa), exhibiting faceted, cauliflower-like and six-fold pyramid-like microstructure, respectively. The maximum R_dep of 〈111〉- and 〈110〉-oriented β-SiC bulks were 3600 and 1300 μm/h at, respectively. The activation energy obtained by the plot of lgR_dep-T_dep⁻¹ is 170 to 280 kJ mol⁻¹, showing an exponential relation with P_Si. The Vickers micro-hardness of β-SiC bulks increased with increasing P_tot and showed the highest value of 35 GPa at P_tot = 40 kPa with a complete 〈111〉 orientation.     

Electrophoretic deposition of titania–carbon nanotubes nanocomposite coatings in different alcohols

The suspensions of titania nanoparticles in different alcohols (methanol, ethanol and butanol) were prepared using triethanolamine (TEA) as a dispersant. The optimum concentration of TEA was 16.67, 8 and 0.33 mL/L in methanol, ethanol and butanol, respectively. Two component suspensions of titania (20 g/L) and carbon nanotubes (CNTs) (0.1, 0.2, 0.5 and 1 g/L) were prepared in different alcohols without and with optimum concentration of TEA. The finer and positively charged titania nanoparticles were heterocoagulated on the surface of coarser and negatively charged CNTs and generated the titania–CNT composite particles with the net positive charge. In the presence of TEA, titania nanoparticles completely covered CNTs surface due to their higher positive surface charge. At same CNT concentration, the deposition rate was faster for suspensions with TEA additive due to the faster mobility of the composite particles. The photocatalysis efficiency of coatings for methylene blue degradation increased as CNTs were incorporated in their microstructure.     

Growth and microstructure of Ba β-alumina films by laser chemical vapor deposition

Ba β-alumina films were prepared by laser chemical vapor deposition. Mostly single-phase Ba β-alumina films were obtained at 1125–1200 K and for an Al/Ba molar ratio of 12.4–16.6. BaAl₂O₄ and α-Al₂O₃ were codeposited with Ba β-alumina under Ba- and Al-rich conditions, respectively. The Ba β-alumina films consisted of hexagonal grains, and the (1 1 0)-oriented Ba β-alumina films had a fin-like columnar structure. The highest deposition rate reached 120 μm h^?1 at around 1200 K. A thin layer of Ba-rich superstructure was formed on the surface of the (1 1 0)-oriented columnar grains.     

Effect of carbon nanotubes on sintering behavior of alumina prepared by sol–gel method

Alumina (Al2O3)/carbon nanotube (CNT) (99/1 by weight) composite was prepared by mixing CNT dispersion with AlCl₃-based gel, followed by high temperature sintering at a temperature up to 1150 °C in argon. Composite alumina precursor showed phase transition order from amorphous to γ-Al₂O₃ after sintered at 900 °C for 2 h, partially to θ-Al₂O₃ after sintered at 1000 °C for 2 h, and then partially to α-Al₂O₃ after sintered at 1150 °C for 2 h. By comparison, control alumina precursor directly transformed from amorphous to α-Al₂O₃ after sintered at a relatively low temperature of 600 °C for 2 h. Composite alumina showed porous structure with pore diameter ranging from 100 nm to 2 µm, whereas control alumina was relatively pore-free. The elevated alumina-crystal phase transition temperatures and the formation of porous structure were ascribed to the presence of CNTs in alumina precursor. The composite alumina sintered at 900 °C for 2 h containing only γ-Al₂O₃ had a BET surface area of 138 m²/g, which was significantly higher than that of control alumina sintered at 1150 °C for 2 h containing only α-Al₂O₃, ~15 m²/g.