Differences between carbon nanofibers produced using Fe and Ni catalysts in a floating catalyst reactor

Carbon nanofibers were produced by the catalytic CVD process by the floating catalyst method, in semi-industrial systems at temperatures above 1350 K. Iron-derived carbon nanofibers were produced from natural gas and xylene, using ferrocene as catalyst source, yielding a thickened submicron vapor grown carbon fibers with a core of multi-wall nanotubes. For the production of Ni derived nanofibers, natural gas was used as the carbon feedstock, and the Ni was added in a nickel compound solution. When no sulfur is used, only soot was obtained, but when sulfur is added to the reactive feedstock, a highly graphitic and very nice stacked-cup-type nanofibers with no free-CVD thickened layer were produced. TEM-EDS analysis confirms that this type of stacked-cup carbon nanofiber is produced only with a partially molten catalyst and methane as hydrocarbon source. In fact, very few fibers have either a particle tip at the end or trapped metal particle inside the wide hollow core of this type of produced carbon material.     

The graphitization of carbon nanofibers produced by the catalytic decomposition of natural gas

Fishbone carbon nanofibers (CNFs) were produced by methane decomposition in a fluidized bed reactor using nickel-copper based catalysts that were prepared with different promoters (SiO₂, Al₂O₃, TiO₂, MgO). The CNFs were subjected to heat treatment (HT) in the temperature range 2400-2800 °C to explore their ability to graphitize. The influence of treatment temperature and CNF metal content on the structural and textural parameters of the resulting heat treated carbon nanofibers was studied. More-ordering was achieved in CNFs containing Si and Ti because of the catalytic effect of these metals. Since titanium carbide appeared after the HT, the formation of graphitic material by carbide decomposition seems to be a plausible mechanism to explain the catalytic graphitization of the CNFs. A parallel evolution of the structural and textural properties of the nanofibers during HT was found, suggesting that a decrease of the specific surface area is caused by the removal of structural defects and an increase of crystallite size.     

The effect of graphitization temperature on the structure of helical-ribbon carbon nanofibers

Structural rearrangement of helical-ribbon carbon nanofibers (CNFs) was studied as a function of graphitization temperature. The as-produced nanofibers are composed of a helical ribbon of graphene spiralled about and angled to the fiber axis. The discrete layers of graphene ribbon overlap each other forming the helical-ribbon in contrast to the discontinuous cones of the more common stacked-cup CNF morphology. After heat treatment to 2400 °C and above, the CNFs were completely free of residual metal catalyst inclusions, principally nickel used in their synthesis, and other functionalities. The formation of loops at the graphene edges was also observed. Heat treatment through the temperature range 1500-2800 °C resulted in a relatively minor contraction in interlayer spacing d₀₀₂ from 0.3381 to 0.3363 nm. This was attributed to the highly graphitic character of the as-produced CNFs. However, there were significant increases in the crystallite thickness L_c through this temperature range. In addition, heat treatment above 2400 °C induced a marked change of the nanofiber morphology from circular to faceted polygonal cross-section resulting from the re-ordering of the turbostratic, curved graphene layers to regions of planar graphene layers with 3-dimensional graphitic structure (AB stacking).     

Effect of ethane addition on propane pyrolysis

Pyrolysis of propane/argon mixture in the presence of trace quantities (0.1% and 0.9%) of ethane was investigated at reflected shock wave temperatures between 1200 and 2000K. Traces of ethane accelerated propane decomposition at high temperature. However, increase in the quantity of ethane added to propane/argon mixture did not result in the same increase of its accelerating influence. Ethylene, methane and acetylene were the main hydrocarbon reaction products, with small quantities of propylene and ethane detected only at lower temperatures. Below 1500K, addition of ethane slightly enhanced the yields of ethylene and methane at the expense of propylene and ethane respectively. The selectivity for acetylene increased with increasing temperature and with the decline of those for the other products. For none of the products, did the presence of ethane alter the relationship between product formation rates and temperature. The influence of ethane addition on propane pyrolysis at high temperatures was explained in terms of increased radical concentrations, especially hydrogen atoms and vinyl radicals, formed at high conversions. These accounted for the rapid acceleration of propane decomposition and the high yield of acetylene at high temperatures.     

Kinetics of the deposition of pyrolytic carbon on nickel

The kinetics of the deposition of laminar graphite on nickel by the pyrolysis of methane, ethane and ethylene at temperatures from 700–1000° has been studied. Two types of graphitic deposit are identified. Continuous films of laminar graphite are formed at higher temperatures, to a weight limit corresponding to the solubility of carbon in nickel at that temperature. It is concluded that such deposits are formed only as a result of a dissolution-precipitation mechanism. Deposits consisting of islands of graphite in a uniform graphite matrix are formed at lower temperatures. The kinetics of deposition are complex, but qualitative agreement is obtained with a model based on the surface aggregation of carbon atoms to account for island nucleation.     

Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.     

Catalytic characteristics of carbon black for decomposition of ethane

The catalytic activities of rubber, color and conductive carbon black catalysts for decomposition of ethane were investigated in the temperature range from 973 to 1173 K. Significantly higher ethane conversion and lower ethylene selectivity were obtained in the presence of carbon black catalysts compared with non-catalytic decomposition, resulting in much higher hydrogen yields. This indicates that carbon black catalysts are effective catalysts for dehydrogenation of ethane to hydrogen and ethylene, as well as for the subsequent decomposition of ethylene to hydrogen and solid carbon. However, more methane was produced in the presence of carbon black catalysts than in non-catalytic decomposition. A reaction mechanism was proposed for the catalytic decomposition of ethane. The hydrogen yield increased with an increase in the specific surface area of the nonporous rubber and color carbon black catalysts with a surface area of up to approximately 100 m²/g. However, the hydrogen yield over the carbon black catalysts with higher surface areas, including the conductive carbon black catalysts with very high surface areas, did not increase significantly. The carbon black catalysts exhibited stable activity for ethane decomposition and hydrogen production for 36 h despite carbon deposition.     

不同结构微反应器下甲烷水蒸气重整制氢性能对比

微通道反应器是便携式制氢领域目前最有发展前景的技术之一。为了提高甲烷水蒸气重整在微反应器内制氢的效果,设计了三种不同结构的微反应器几何模型,分别为直管(Pipe)模型、平板圆弧弯道(FCC)模型和三纹内螺旋枪管(Tri-g ISB)模型,利用Ansys Fluent流体仿真软件结合甲烷水蒸气重整制氢的CHEMKIN反应机理文件对三种不同结构的微反应器进行了数值模拟分析。通过研究不同条件下微反应器出口气体组分变化可知,入口速度越小,CH₄转化率和H₂体积分数越高;S/C>3时,CH₄转化率增大至80%以上、H₂含量增加至73vol%以上;壁面温度越大,CH₄转化率可稳定在99.9%,几乎完全转化,H₂含量增大到77vol%以上,但温度过高会降低H₂产量,增加CO含量。通过计算不同条件下微反应器达到稳定所需时间可知,随入口速度和S/C增加稳定时间均逐渐减小并趋于稳定,随壁面温度增加,稳定时间先减小后增加。通过对比三种微反应器可知,复...     

A conceptual model for the structure of catalytically grown carbon nano-fibers

Typical platelet-type, herringbone-type, and tubular-type carbon nano-fibers (CNF) were catalytically prepared through three distinctly different routes. By comprehensive observations using SEM, TEM, STM, and XRD, these CNFs were found to have common sub-structures, which we call carbon nano-rods (CNR) and carbon nano-plates (CNP). A CNR was a carbon cluster of 8-10 graphene layers with unique diameters of about 2.5 nm and variable lengths in the range of 15-100 nm. CNPs appeared to be sets of 5-25 graphene stacks, probably formed by association of several CNRs. The faceted catalyst surfaces determine the particular ordered arrangements of the CNRs or CNPs in the final fiber form that result in the production of platelet, herringbone, or tubular-type CNFs. The diameters of the CNFs were defined by the length of the CNR and CNP sub-units (or a series of these) and their angles of association relative to the fiber axis. Graphitization at high temperatures closed the ends (edges) of carbon hexagons in CNRs to form concentrically layered dome-like caps on the surface of CNFs. Such sub-structure units can be separated by grinding.     

Study of the influence of pressure on enhanced gaseous hydrocarbon yield under high pressure-high temperature coal pyrolysis

The influence of pressure on the yield of gaseous hydrocarbon products derived from pyrolysis of Fushun and Xianfeng coals have been investigated in an anhydrous and confined system. Pyrolysis was performed in sealed gold tubes at 380 °C and under the pressures ranging from 50 to 250 MPa for 24 h. The results show that the effect of pressure on coal pyrolysis and product generation should not be ignored. For the Fushun and Xianfeng lignite, the yields of gaseous hydrocarbon generation increase by 9.1% and 12.7% when the pressure increases from 50 to 250 MPa, respectively. However, the yields of hydrogen gas decrease greatly with pressure. The hydrogen gas yields of Fushun and Xianfeng lignite decrease by 76.5% and 75.9%, respectively, when the pressure increases from 50 to 250 MPa. Yields of carbon dioxide gas of Fushun and Xianfeng coals were enhanced with increasing pressure by 7.4% and 8.9% respectively. Data of stable carbon isotope compositions reveal that the methane and ethane carbon isotope values are also affected by pressure, as they become heavier by approximately 1.2‰ (PDB) when the pressure is increased from 50 to 250 MPa. Simultaneously, the hydrogen isotope compositions of methane and ethane increase by 10.3‰ and 7.1‰, respectively. Our experimental results suggest that the increase in gaseous hydrocarbon yield is resulted from synthesis of carbon dioxide and hydrogen and pressure serves to facilitate the synthetic process.     

Flame synthesis of carbon nanofibers on carbon paper: Physicochemical characterization and application as catalyst support for methanol oxidation

We developed a simple, rapid and highly efficient flame synthesis method for direct growing carbon nanofibers (CNFs) on carbon paper (CP) using a common laboratory ethanol flame as both heat and carbon sources. High density CNFs with tangled solid-cored structure were uniformly formed over the Ni-plated CP surface in ∼20 s. The morphologies of the CNFs were characterized by scanning electron microscopy and transmission electron microscopy. X-ray diffraction study revealed the graphitic nature of the CNFs. Raman spectroscopy analysis confirmed that the CNFs are disordered graphitic nanocrystallites with high degree of exposed edges. Electrochemical impedance spectroscopy and cyclic voltammetry were used to show that growing CNFs directly on CP facilitates electron transfer with concomitant increase in double-layer capacitance. The CNF/CP was used as support for Pt nanoparticles to study their supporting effect on the catalyst performance. The as prepared Pt/CNF electrocatalyst exhibited much improved electrocatalytic activity for methanol oxidation compared to Pt/CP and commercial Pt/C on CP. High electronic conductivity and improved electrochemical behavior of the CNF/CPs, resulted from direct contact of the nanofibers with CP, combined with unique properties of CNFs, make the synthesized CNF/CPs promising for fuel cell applications.     

Graphitization thermal treatment of carbon nanofibers

Carbon nanofibers (CNFs) and carbon nanotubes have revolutionized the world of the nanotechnology due to their excellent mechanical, electrical and thermal properties. CNFs are graphitic fibers made of stacks of graphene layers aligned perpendicular, tilted or parallel to the fiber axis, thus resulting in different microstructures. Post-production treatments can be applied to CNFs to improve their performance in several applications. Among them, the heat treatment at high temperature to achieve the transformation of the CNFs into graphite (graphitization) or graphitized CNFs (graphitization heat treatment) has been studied in detail. This review covers the literature on this topic for the last 20 years, analyzing the structural and textural changes shown by the CNFs during graphitization, and how these changes influence their mechanical and electrical properties. Different techniques, particularly, high-resolution transmission electron microscopy, have allowed to determine the microstructure of these nanofilaments. A survey of the applications of graphitized CNFs is provided, these including additives for polymer reinforcement in composites, anodes in lithium-ion batteries, catalyst supports in fuel cells, hydrogen storage and others such as potential biosensors and catalysts in diverse reactions. In this regard, special emphasis is placed on the advantages (or disadvantages) of using graphitized CNFs instead of as-grown CNFs.     

Preparation of highly crystalline nanofibers on Fe and Fe-Ni catalysts with a variety of graphene plane alignments

The present study confirmed that highly crystalline nanofibers with controlled structure may be prepared over Fe and Fe-Ni alloy catalysts. The degree of graphitization of various carbon nanofibers (CNFs) was analyzed by using C(0 0 2) peaks from the XRD profiles. The C(0 0 2) peaks of CNFs over Fe catalyst shifted to higher angle and became narrower as the preparation temperature increased from 560 to 620 °C. Tubular CNFs prepared at temperature higher than 630 °C showed lower 2θ angles compared to those of platelet fibers. CNFs prepared over Fe-Ni catalysts tended to resemble those prepared over Fe catalysts. The degree of graphitization of platelet CNFs resembled natural graphite, while d_0 0 2 of the tubular CNFs showed values below the 3.39 Å reported as a theoretical minimum for a cylindrical alignment. Lc_0 0 2 of platelet and tubular CNFs increased by heat treatment at 2000 and 2800 °C though d_0 0 2 changed little. A transverse section of platelet and tubular CNFs had a hexagonal shape, not a round shape. The hexagonal column allows AB stacking of hexagonal planes that can give perfect hexagonal alignment.     

Evaluation of the use of different hydrocarbon fuels for gas reburning

Gas reburning is a NO_x reduction technique that has been demonstrated to be efficient in different combustion systems. An experimental study of gas reburning performance in the low temperature range (at and under 1100°C) has been carried out. An evaluation of the use of different hydrocarbon fuels, such as natural gas, methane, ethane, ethylene and acetylene was performed and the influence of the temperature and stoichiometry is considered. The results show that the reburning process is effective under appropriate conditions at the low temperatures used in this work. However, as the temperature diminishes, the influence of the reburn fuel becomes more marked and the use of acetylene or ethane and ethylene leads to better performance than natural gas or methane, the classical reburn fuels for high temperature applications.     

Microstructure and through-film electrical characteristics of vertically aligned amorphous carbon films

The microstructure and electrical properties of in-situ annealed carbon films is studied in this paper. In-situ annealing (150 °C to 600 °C) was done during the deposition of carbon films with −300 V substrate bias. Transmission electron microscopy and two points electrical probing studies were performed and the deduced transition for vertical orientated graphitic planes occurs at temperatures above 400 °C. The microstructure of the films strongly depends on the deposition temperature of the films (room temperature, 400 °C and 600 °C). Electrical conductivity of the film strongly depends on texturing due to the formation of preferred orientation in the vertical direction. The vertically orientated carbon (VOC) sheet provides effective nanochannels for electron transport, thus significantly improves the electrical properties of the annealed film.     

Experimental measurements and computer simulation of methane adsorption on activated carbon fibers

Three activated carbon fibers (ACFs) with different BET specific surface areas (SSAs) were prepared. Experimental characterization and methane adsorption on the ACFs were measured by the intelligent gravimetric analyzer (IGA-003, Hiden) at 258 and 298 K. Correlations proposed between the methane adsorption capacity and SSA indicate that the SSA plays an important role on storage amount at a given temperature. A detailed experimental investigation was focused on the sample ACF3 of the highest SSF of 1511 m²/g at five temperatures, from 258 to 298 K. The temperature dependence for methane adsorption amount on ACF3 at 1.8 MPa is proposed. It shows that temperature is vital to methane storage capacity for ACF3, and adsorption storage at the temperatures below 280 K is recommended for favorite uptakes. To model ACF3, the pores are described as slit-shaped with a pore size distribution that was determined by molecular simulation and the statistics integral equation. Predictions of methane adsorption, carried out at 258 and 298 K and high pressures by molecular simulation, indicate that our sample ACF3 can reach the uptake of 14.99 wt% at 4.0 MPa and 298 K, which is comparable with the best result in the literature.     

CVD production of double-wall and triple-wall carbon nanotubes

Carbon nanotubes with a drastically reduced number of graphitic layers were synthesized in high yield by chemical vapor deposition of methane over a sol–gel Mo–Co catalyst supported on magnesium oxide particles. We show that both the catalyst composition and the methane flow rate strongly influence the porosity of the catalyst support, the catalyst dispersion, the degree of aromatization of the hydrocarbon feedstock as well as the degree of carbon deposition, and thus can be used efficiently to control the number of graphitic layers of the grown carbon nanotubes. A low content of molybdenum in the catalyst combined with a low methane flow rate especially leads to the formation of thin-wall carbon nanotube materials which are predominantly composed of double- and triple-wall carbon nanotubes. These types of carbon nanotubes are of special interest as reinforcement components in the field of advanced composite materials.     

Open-air carbon coatings on fused quartz by laser-induced chemical vapor deposition

Carbon films are deposited on fused quartz substrates by CO₂ laser-induced chemical vapor deposition (LCVD) using a novel open-air coating system. The hydrocarbon precursor gases are methane, propane and butane. The deposition rates of the three hydrocarbon gases are determined by measuring the mass of the carbon film deposited at constant temperature, and validated by film thickness measurements obtained using an environmental scanning electron microscope. The results indicate that butane and propane have significant deposition at 1375-1500 K, while deposition starts at 1550 K for methane. All three hydrocarbons have an exponential increase in deposition rate. Deposition rates obtained with butane and propane show a much stronger influence of temperature compared to methane. Raman spectra of deposited carbon films indicate that the surface consists of glass-like or nanocrystalline carbon. The ratio of D-peak to G-peak Raman band intensities decreases as the deposition temperature is increased, which is possibly due to self-annealing and additional surface reaction during high temperature deposition. This finding indicates that the carbon film exhibits higher structural order at high deposition temperatures, which can significantly enhance the film’s hermeticity and mechanical properties for use as an optical fiber coating.     

Orientation of graphitic planes during annealing of “dip deposited” amorphous carbon film: A carbon K-edge X-ray absorption near-edge study

Annealing effect of amorphous carbon thin films on Si(1 0 0) substrates is studied by normal incidence and angle dependent carbon K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The angle dependence of the XANES signal shows that the graphitic basal planes are oriented perpendicular to the surface when the film is annealed at 1000 °C. Micro-Raman spectroscopy reveals two well-separated bands the D band at 1355 cm⁻¹ and G band at ∼1600 cm⁻¹, and their I_D/I_G intensity ratio indicates the formation of more graphitic film at higher annealing temperatures. X-ray diffraction pattern of 1000 °C temperature annealed film confirms the formation of graphite structure.     

Growth of mechanically fixed and isolated vertically aligned carbon nanotubes and nanofibers by DC plasma-enhanced hot filament chemical vapor deposition

Vertically aligned, mechanically isolated, multiwalled carbon nanotubes (MWCNTs) and nanofibers (MWCNFs) were grown using an array of catalyst nickel nanowires embedded in an anodic aluminum oxide (AAO) nanopore template using DC plasma-enhanced hot filament chemical vapor deposition (HFCVD). The nickel nanowire array, prepared by electrodeposition of nickel into the pores of a commercially available AAO membrane, acts as a template for CNT and CNF growth. It also provides both a mechanical “fixed support” boundary condition and enforces sufficient spatial separation of the CNT/CNFs from each other to enable reliable and well-controlled mechanical testing of individual vertically aligned CNT/CNFs. In contrast with other AAO-templated growth methods, no post-growth etching of the AAO is required, since the CNTs/CNFs grow out of the pores and remain vertically aligned. A mixture of hydrogen and methane was used for the growth, with hydrogen acting as a dilution and source gas for the DC plasma, and methane as the carbon source. A negative bias was applied to the sample mount to generate the DC plasma. The filaments provided the necessary heat for dissociation of molecular species, and also heat the sample itself significantly. Both of these effects assist the CNT/CNF growth. Minimal heating came from the low-power plasma. However, the associated DC field was essential for the vertical alignment of the CNTs and CNFs. Scanning electron, transmission electron, and atomic force microscopy confirm that the CNT/CNFs are composed of graphitic layers, and form a vertically aligned, relatively uniform, and dense array across the AAO template. A significant number of the structures grown are indeed high quality nanotubes, as opposed to more defective nanofibers that are often predominant in other growth methods. This method has the advantage of being scalable and consuming less power than other techniques that grow vertically aligned CNTs/CNFs.