High surface area carbon aerogels as porous substrates for direct growth of carbon nanotubes

Novel carbon composites are fabricated through catalyzed CVD growth of carbon nanotubes directly on the inner surfaces of monolithic carbon aerogel (CA) substrates. Uniform CNT yield is obtained throughout the internal pore volume of CA monoliths with macroscopic dimensions. These composites possess large surface areas (>1000 m(2) g(-1)) and exhibit enhanced electrical conductivity following CNT growth.     

Synthesis of carbon encapsulated magnetic nanoparticles with giant coercivity by a spray pyrolysis approach

Carbon encapsulated magnetic (metal) nanoparticles (CEMNPs) have wide applications in biomedicine and the magnetic recording industry. However, synthesis of such particles with a high coercive force and good ferromagnetism is still a great challenge. The present study reports a new method for the continuous production of CEMNPs of high purity. This involves the spray pyrolysis of a mixture of iron pentacarbonyl and ethanol at 500-900 degrees C. Results show that the Fe (or Fe3C) particles synthesized at 700 and 900 degrees C were well encapsulated by graphitic layers with rare byproducts such as carbon nanotubes, nanofibers, or bulk amorphous carbon. Those synthesized at 700 degrees C had a particle size of 30-50 nm, a giant coercive force of 867 Oe, and a good magnetic remanence of 33% at room temperature. The present approach based on spray pyrolysis is advantageous over previous ones in suitability for large-scale production, and the synthesized material has wide applications in many fields.     

Cobalt ultrathin film catalyzed ethanol chemical vapor deposition of single-walled carbon nanotubes

We report a simple and efficient chemical vapor deposition (CVD) process that can grow oriented and long single-walled carbon nanotubes (SWNTs) using a cobalt ultrathin film ( approximately 1 nm) as the catalyst and ethanol as carbon feedstock. In the process, millimeter- to centimeter-long, oriented and high-quality SWNTs can grow horizontally on various flat substrate surfaces, traverse slits as large as hundreds of micrometers wide, or grow over vertical barriers as high as 20 microm. Such observations demonstrate that the carbon nanotubes are suspended in the gas flow during the growth. The trace amount of self-contained water (0.2-5 wt %) in ethanol may act as a mild oxidizer to clean the nanotubes and to elongate the lifetime of the catalysts, but no yield improvement was observed at the CVD temperature of 850 degrees C. We found that tilting the substrates supporting the Co ultrathin film catalysts can grow more, longer carbon nanotubes. A mechanism is discussed for the growth of long SWNTs.     

Improvement of Fe/MgO catalysts by calcination for the growth of single- and double-walled carbon nanotubes

Calcination at 900-1000 degrees C for 8-12 h of an Fe/MgO catalyst prepared by impregnation was found to result in a uniform MgFe2O4/MgO solid solution that showed a successful settling of well-dispersed iron species into the MgO lattice. During methane reduction, many iron-containing particles with a diameter of about 4 nm were formed on the catalyst surface to provide numerous active sites for the growth of single- and double-walled carbon nanotubes. There was a significant improvement of the Fe/MgO catalyst that resulted in a high yield of impurity-free nanotubes. Using C2H4 cracking at 600 degrees C and transmission electron microscope observations, the Fe species distribution in the catalysts and microscope images of nanotube growth were described in detail. H2 reduction of the calcined Fe/MgO catalyst was found to cause the formation of iron layers on the catalyst surface, which resulted in the growth of only carbon layers. The results are useful for understanding changes in the metal species distribution in the catalysts and the nanotube growth mechanism, and they provide a simple method to improve Fe/MgO catalysts.     

Formation of graphitic structures in cobalt- and nickel-doped carbon aerogels

We have prepared carbon aerogels (CAs) doped with cobalt or nickel through sol-gel polymerization of formaldehyde with the potassium salt of 2,4-dihydroxybenzoic acid, followed by ion exchange with M(NO3)2 (where M = Co2+ or Ni2+), supercritical drying with liquid CO2, and carbonization at temperatures between 400 and 1050 degrees C under a N2 atmosphere. The nanostructures of these metal-doped carbon aerogels were characterized by elemental analysis, nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Metallic nickel and cobalt nanoparticles are generated during the carbonization process at about 400 and 450 degrees C, respectively, forming nanoparticles that are approximately 4 nm in diameter. The sizes and size dispersion of the metal particles increase with increasing carbonization temperatures for both materials. The carbon frameworks of the Ni- and Co-doped aerogels carbonized below 600 degrees C mainly consist of interconnected carbon particles with a size of 15-30 nm. When the samples are pyrolyzed at 1050 degrees C, the growth of graphitic nanoribbons with different curvatures is observed in the Ni- and Co-doped carbon aerogel materials. The distance of graphite layers in the nanoribbons is approximately 0.38 nm. These metal-doped CAs retain the overall open cell structure of metal-free CAs, exhibiting high surface areas and pore diameters in the micro- and mesoporic region.     

Dendrimer-assisted low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition

Using a shielded growth approach and N2-annealed, nearly monodispersed Fe2O3 nanoparticles synthesized by interdendritic stabilization of Fe3+ species within fourth-generation poly(amidoamine) dendrimers, carbon nanotubes and nanofibers were successfully grown at low substrate temperatures (200-400 degrees C) by microwave plasma-enhanced chemical vapor deposition.     

Incorporation, oxidation and pyrolysis of ferrocene into porous silica glass: a route to different silica/carbon and silica/iron oxide nanocomposites

This work reports the incorporation of ferrocene into a porous silica glass under ambient temperature and atmosphere. After or during the ferrocene incorporation, the spontaneous formation of ferricinium ions was observed by electron paramagnetic resonance (EPR), UV-visible, X-ray absorption near-edge structure (XANES), and 57Fe M?ssbauer measurements. It was shown that the oxidation of ferrocene molecules to ferricinium ions was promoted by air and that the Si-O- groups on the surface of the pores act as counteranions. Pyrolysis of the porous glass/ferricinium material under argon atmosphere and variable temperature yields different glass/carbon nanocomposites, which were subsequently treated with an HF solution in order to remove the glassy fraction. The resulting insoluble carbon materials were characterized by transmission electron microscopy (TEM), Raman, and EPR spectroscopy and consisted of amorphous carbon when the pyrolysis was carried out at 900 or 1000 degrees C and of a mixture of carbon nanotubes and carbonaceous materials at a pyrolysis temperature of 1100 degrees C. When the pyrolysis was conducted under air, the incorporated ferricinium forms alpha-Fe2O3, and the resulting material is a transparent and highly homogeneous glass/iron oxide nanocomposite.     

Fe/Co alloys for the catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes (CNTs). 1. The CNT-Fe/Co-MgO system

Mg(0.90)Fe(x)Co(y)O (x + y = 0.1) solid solutions were synthesized by the ureic combustion route. Upon reduction at 1000 degrees C in H2-CH4 of these powders, Fe/Co alloy nanoparticles are formed, which are involved in the formation of carbon nanotubes, which are mostly single and double walled, with an average diameter close to 2.5 nm. Characterizations of the materials are performed using 57Fe M?ssbauer spectroscopy and electron microscopy, and a well-established macroscopic method, based on specific-surface-area measurements, was applied to quantify the carbon quality and the nanotubes quantity. A detailed investigation of the Fe/Co alloys' formation and composition is reported. An increasing fraction of Co2+ ions hinders the dissolution of iron in the MgO lattice and favors the formation of MgFe2O4-like particles in the oxide powders. Upon reduction, these particles form alpha-Fe/Co particles with a size and composition (close to Fe(0.50)Co(0.50)) adequate for the increased production of carbon nanotubes. However, larger particles are also produced resulting in the formation of undesirable carbon species. The highest CNT quantity and carbon quality are eventually obtained upon reduction of the iron-free Mg(0.90)Co(0.10)O solid solution, in the absence of clusters of metal ions in the starting material.     

Vertical array growth of small diameter single-walled carbon nanotubes

A hot filament chemical vapor deposition method has been developed to grow vertical array single-walled carbon nanotubes (SWNTs). In this study, a hot filament (temperature greater than 2000 degrees C) was used to activate gas mixtures of hydrogen and carbon containing species at sub-atmospheric pressures. Silicon substrates decorated with islands of iron were directly inserted into a preheated furnace in which a hot filament is activating the gas. Vertical arrays of SWNTs are produced with diameters ranging from 0.78 to 1.6 nm. The samples were characterized with Raman and fluorescence spectroscopy and SEM and TEM microscopy.     

Synthesis of multi-walled carbon nanotubes catalyzed by substituted ferrocenes

A range of substituted ferrocenes were used as catalysts for the synthesis of multi-walled carbon nanotubes (MWCNTs) and carbon fibers (CFs). These products were obtained in the temperature range 800-1000 °C, in a reducing atmosphere of 5% H₂ by pyrolysis of (CpR)(CpR′)Fe (R and R′ = H, Me, Et and COMe) in toluene solution. The effect of pyrolysis temperature (800-1000 °C), catalyst concentration (5 and 10 wt.% in toluene) and solution injection rate (0.2 and 0.8 ml/min) on the type and yield of carbonaceous product synthesized was investigated. Carbonaceous products formed include graphite film (mostly at high temperature; 900-1000 °C), carbon nanotubes and carbon fibers. The carbonaceous materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The ferrocene ring substituents influenced both the CNT diameter and the carbon product formed.     

Growth control of single and multi-walled carbon nanotubes by thin film catalyst

Single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were synthesized on silicon substrate by the control of catalyst size, hydrocarbon species, and carbon flux through chemical vapor deposition (CVD). Catalysts for SWNTs and MWNTs could be obtained by an agglomeration of sputtered Co–Mo and pure Co thin films, respectively. The addition of Mo in the Co catalyst provides an effective nucleation site for SWNT and the low carbon flux by using methane gas in CVD reaction makes it possible to grow a single-walled structure.     

Synthesis and characterization of monolithic carbon aerogel nanocomposites containing double-walled carbon nanotubes

We report the synthesis and characterization for the first examples of monolithic low-density carbon aerogel (CA) nanocomposites containing double-walled carbon nanotubes. The CA nancomposites were prepared by the sol-gel polymerization of resorcinol and formaldehyde in an aqueous surfactant-stabilized suspension of double-walled carbon nanotubes (DWNTs). The composite hydrogels were then dried with supercritical CO 2 and subsequently carbonized under an inert atmosphere to yield monolithic CA structures containing uniform dispersions of DWNTs. The microstructures and electrical conductivities of these CA nanocomposites were evaluated for different DWNT loadings. These materials exhibited high BET surface areas (>500 m (2)/g) and enhanced electrical conductivities relative to pristine CAs. The details of these results are discussed in comparison with theory and literature.     

Selective matching of catalyst element and carbon source in single-walled carbon nanotube synthesis on silicon substrates

We have studied the compatibility of various catalysts for ethylene and ethanol chemical vapor deposition (CVD) syntheses of single-walled carbon nanotubes (SWNTs) on Si substrates. A strong selectivity between the catalyst elemental species and carbon source was found; SWNT yield for Fe (Co) catalysts was much higher for ethylene (ethanol) CVD than for ethanol (ethylene) CVD. This strong and completely opposite selectivity implies significantly different SWNT growth mechanisms for ethanol and ethylene CVD on Si substrates.     

Thermal decomposition of ferrocene as a method for production of single-walled carbon nanotubes without additional carbon sources

A new method to grow bulk quantities of single-walled carbon nanotubes (SWCNTs) by a catalytic chemical vapor deposition (CVD) process with the possibility of varying the pressure has been developed and is reported in this paper. Thermal decomposition of ferrocene provides both catalytic particles and carbon sources for SWCNT growth using Ar as a carrier gas. Upon an increase in the pressure, the mean diameter of the SWCNTs decreases. In fact, high abundances of SWCNT with diameters as small as 0.7 nm, which is the limit for stable caps with isolated pentagons, can be obtained. An additional advantage of this method is that as no external carbon sources are required, SWCNT synthesis can be achieved at temperatures as low as 650 degrees C.     

Surface properties of porous carbon obtained from polystyrene sulfonic acid-based organic salts

Pyrolysis ofpolysterene sulfonic acid-co-maleic acid salts at 800 degrees C resulted in formation of new materials consisting of porous carbon and metal species dispersed on the surface. After hydrochloric acid treatment, the metal oxides/salts were removed. Obtained materials were characterized using adsorption of nitrogen, thermogravimetric analysis, Raman spectroscopy, and scanning electron microscopy with energy dispersive analysis of X-rays. The results showed highly developed porous structures in the range of micro- and mesopores. The porous features of new materials resemble those characteristics for carbon foams. The differences in the porous structure are linked to the type of transition metal used for the modification of the initial polymer and the chelation process. Macro- and mesopores are spherical/cylindrical in shape, and they are likely formed when release of pyrolysis gases, such as CO2, NO2, SO2, H2S, and CxHy, occurs. Moreover, reduction of metal, its migration to the surface, and agglomeration contribute to development of porosity. Depending on the reactivity of the metal used for cation exchange (Fe, Co, or Ni) either sulfides (nickel and cobalt) or oxides (cobalt and iron) are formed on the carbon surface.     

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.     

Polypropylene/carbon nanotube magnetic composites obtained using carbon nanotubes from sawdust

Magnetic polypropylene (PP) nanocomposites with different loadings (from 0.5 to 20 wt %) of carbon nanotubes with iron (CNT‐Fe) were fabricated using the melt‐mixing method. The carbon nanotubes were synthesized by pyrolysis of sawdust from the furniture industry. The morphological characterization shows homogenous dispersion of the filler in the polymer matrix. The addition of only 0.5 wt % CNT‐Fe already results in ferromagnetic behavior in the diamagnetic polymer matrix. The thermal properties were investigated using thermogravimetric analysis and differential scanning calorimetry. The results show an increase in the maximum degradation, crystallization, and melting temperatures of the nanocomposites compared with neat PP. The nanocomposites showed improvement in terms of mechanical and oxygen permeability properties. A very significant result of the work is the high remnant magnetization and coercivity values of the nanocomposites at room temperature whereas most of the works on similar systems show magnetic properties only at very low temperatures.     

Ceramic microreactors for on-site hydrogen production from high temperature steam reforming of propane

The steam reforming of hydrocarbon fuels is a promising method for the production of hydrogen for portable electrical power sources. A suitable reactor for this application, however, must be compatible with temperatures above 800 degrees C to avoid coking of the catalytic structures during the reforming process. Here, ceramic microreactors comprising high surface area, tailored macroporous SiC porous monoliths coated with ruthenium (Ru) catalyst and integrated within high-density alumina reactor housings were used for the steam reforming of propane into hydrogen at temperatures between 800 and 1000 degrees C. We characterized these microreactors by studying C3H8 conversion, H2 selectivity, and product stream composition as a function of the total inlet flow rate, steam-to-carbon ratio (S/C), and temperature. As much as 18.2 sccm H2, or 3.3 x 104 sccm H2 per cm3 of monolith volume, was obtained from a 3.5 sccm entering stream of C3H8 at a S/C of 1.095 and temperatures greater than 900 degrees C. Operating at a S/C close to 1 reduces the energy required to heat excess steam to the reaction temperature and improves the overall thermal efficiency of the fuel processor. Kinetic analysis using a power law model showed reaction orders of 0.50 and -0.23 with respect to propane and steam, respectively, indicating that the rate limiting step in the steam reforming reaction is the dissociative adsorption of propane on the Ru catalyst. The performance of the microreactor was not affected after exposure to more than 15 thermal cycles at temperatures as high as 1000 degrees C, and no catalyst deactivation was observed after more than 120 h of continuous operation at 800 degrees C, making these ceramic microreactors promising for efficient on-site hydrogen production from hydrocarbons for use in polymer electrolyte membrane (PEM) fuel cells.     

Molding versus dispersion: effect of the preparation procedure on the capacitive and cycle life of carbon nanotubes aerogel composites

Binderless carbon nanotubes aerogel (CNAG) composites represent a new class of high-performing electrodes for energy storage applications such as electrochemical double layer capacitors. The composites developed here differ significantly from these previously prepared with dispersion processes. The CNAG material was prepared by a molding procedure that is the synthesis by a chemical vapor deposition method to grow carbon nanotubes directly onto a microfibrous carbon paper substrate. Then the carbon aerogel is synthesized on the carbon nanotubes. The key feature of the method is eliminating the need of controlling the carbon nanotube concentration, which permits optimized dispersion processes to reinforce the aerogel's networks. The CNAG electrode delivered very high specific capacitances of 524 F g⁻¹ in KOH electrolyte and 280 F g⁻¹ in H₂SO₄ electrolyte. Furthermore, this better integration of carbon nanotubes in the matrix of carbon aerogel improved its resistance to the attack by the electrolyte and conferred an excellent cycle life over 5,000 cycles of charge–discharge in both electrolytes.     

Surface area and microporosity of carbon aerogels from gas adsorption and small- and wide-angle X-ray scattering measurements

A carbon aerogel was obtained by carbonization of an organic aerogel prepared by sol-gel polymerization of resorcinol and formaldehyde in water. The carbon aerogel was then CO(2) activated at 800 degrees C to increase its surface area and widen its microporosity. Evolution of these parameters was followed by gas adsorption and small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) with contrast variation by using dry and wet (immersion in benzene and m-xylene) samples. For the original carbon aerogel, the surface area, S(SAXS), obtained by SAXS, is larger than that obtained by gas adsorption (S(ads)). The values become nearly the same as the degree of activation of the carbon aerogel increases. This feature is due to the widening of the narrow microporosity in the carbon aerogel as the degree of activation is increased. In addition, WAXS results show that the short-range spatial correlations into the assemblies of hydrocarbon molecules confined inside the micropores are different from those existing in the liquid phase.