Preparation and lithium storage performance of silicon and carbon microrods by chemical vapor co-deposition

Silicon/carbon microrods are co-deposited on copper substrate and graphite spheres surface using dimethyl dichlorosilance as carbon and silicon precursor. The obtained composites are characterized by X-ray diffraction and scanning electron microscopy. The experimental results show that silicon/carbon microrods deposited on the copper substrate, whose diameter is about 500 nm, are accumulated into sisallike morphology, those deposited on the graphite spheres surface form hedgehog-like feature, whose diameter is about 200 nm and whose top is like cauliflower. When current density of 50 mA/g is applied, charge capacity of silicon/carbon microrods is 1492 mA h/g (deposited on copper substrate) and 693 mA h/g (deposited on the graphite spheres surface). Moreover, silicon/carbon microrods deposited on the graphite spehres and copper substrate respectively deliver the capacity of 592, 985 mA h/g, and display no capacity decay at all after the 20 cycles, when cycled under current density of 500 mA/g.     

Influence of the catalyst type on the growth of carbon nanotubes via methane chemical vapor deposition

The preparation of the catalyst is one of the key parameters which governs the quality of carbon nanotubes (CNTs) grown by catalyzed chemical vapor deposition (CVD). We investigated the influence of three different procedures of catalyst preparation on the type and diameter of CNTs formed under identical growth conditions via methane CVD. In the first one, chemically synthesized colloidal iron oxide or iron molybdenum alloy nanoparticles were used, which were homogeneously deposited on silicon substrates by spin coating to prevent them from coalescence under CVD growth conditions. The obtained multiwall CNTs (MWNTs) exhibited diameters corresponding to the catalyst particle size, whereas no formation of single-wall CNTs (SWNTs) was observed. In the second method, commercial porous alumina nanoparticles were used in association with iron and molybdenum salts and the Fe/Mo catalyst was formed in situ. We determined that the alumina concentration significantly influenced the morphology of the catalyst and that below a critical value of the range of 1 g/L no CNTs were formed. While yielding nearly defect-free SWNTs, their diameter could not be controlled using this procedure, resulting in a large distribution of tube sizes. In a third, new preparation method, associating alumina and iron-based nanoparticles, SWNTs of a different size and narrower diameter distribution as compared to the second method were obtained. Our results are evidence of the essential role of alumina particles in the formation of SWNTs, and the newly developed method opens up a way to the synthesis of diameter-controlled SWNTs via catalyzed CVD.     

Enhancing the pyrolysis of scrap rubber for carbon nanotubes/graphene production via chemical vapor deposition

Carbon nanostructures are considered nowadays as very important materials for both fundamental research and industrial applications because of their well-defined morphologies, which leads to excellent performance in various fields. This study presents the preparation of carbon nanostructures starting from cheap source represented by scrap rubber after pursuing optimized pyrolysis of scrap rubber at 500^oC as deduced from thermal gravimetric analysis (TGA). The resulting cracked hydrocarbons from pyrolysis were collected over a well-designed Fe-Ni-Cu/MgO as catalyst via chemical vapor deposition (CVD), in which a growth temperature of 750^oC was undertaken for 60 min. A further attempt was elaborated where the scrap rubber was exposed to thermal aging at 90^oC for 14 days prior to CVD of its pyrolysis products in order to enhance the cracking process and increase the yield of the lighter hydrocarbons produced which leads to formation of well-defined carbon nanostructures. Characterizations on the produced carbon nanostructures were achieved using transmission electron microscopy (TEM) and Raman spectroscopy. The adsorption of methylene blue on the carbon nanostructures was also studied. The characterizations confirmed that the morphology of the resulting carbon nanostructures derived from scrap rubber without prior thermal aging composed of graphene sheets wrapping carbon nanotubes (CNTs-A). After thermal aging of scrap rubber prior to pyrolysis and CVD, the produced carbon nanostructures composed principally of CNTs (CNTs-B) in a well-defined form in higher yield. The Langmuir model appeared to be best-fitting the adsorption of MB on both samples. High monolayer adsorption capacity of 95 mg MB/g was accomplished in case of CNTs-A versus 60 mg MB/g in case of CNTs-B, respectively. Ultraviolet-Visible (UV-Vis.) spectroscopic study revealed that the presence of MB molecules on the surface of CNTs may enhance the electronic properties of the prepared samples.     

Synthesis of double-walled carbon nanotubes by catalytic chemical vapor deposition and their field emission properties

Double-walled carbon nanotubes (DWCNTs) were synthesized by catalytic chemical vapor deposition using Fe-Mo/MgO as a catalyst at 1000 degrees C under the mixture of methane and hydrogen gas. The nanotubes were purified by acid but were not damaged. Thermogravimetric analysis revealed the purity of the tubes to be about 90%. The high-resolution transmission electron microscopy image showed that DWCNTs have inner tube diameters of 1.4-2.6 nm and outer tube diameters of 2.3-3.4 nm. We observed radial breathing modes in Raman spectra, which are related to the diameter of inner nanotubes. The purified DWCNTs were mixed with organic vehicles and glass frit, and then they were screen-printed on glass substrate coated with indium tin oxide. The field emission properties of the screen-printed DWCNT films were examined by varying the amount of glass frit ingredient within the DWCNT paste. The results showed that DWCNT emitters had good emission properties such as turn-on field of 1.33-1.78 V/microm and high brightness. When the applied anode voltage was gradually increased, current density and brightness became saturated. We also observed DWCNTs adsorbed on the anode plate; they were DWCNTs peeled off from the cathode plate for field emission measurement.     

Magic carbon clusters in the chemical vapor deposition growth of graphene

Ground-state structures of supported C clusters, C(N) (N = 16, ..., 26), on four selected transition metal surfaces [Rh(111), Ru(0001), Ni(111), and Cu(111)] are systematically explored by ab initio calculations. It is found that the core-shell structured C(21), which is a fraction of C(60) possessing three isolated pentagons and C(3v) symmetry, is a very stable magic cluster on all these metal surfaces. Comparison with experimental scanning tunneling microscopy images, dI/dV curves, and cluster heights proves that C(21) is the experimentally observed dominating C precursor in graphene chemical vapor deposition (CVD) growth. The exceptional stability of the C(21) cluster is attributed to its high symmetry, core-shell geometry, and strong binding between edge C atoms and the metal surfaces. Besides, the high barrier of two C(21) clusters' dimerization explains its temperature-dependent behavior in graphene CVD growth.     

Controlling the diameter of carbon nanotubes in chemical vapor deposition method by carbon feeding

It was found that the diameter distribution of single-walled carbon nanotubes (SWNTs) grown by the chemical vapor deposition (CVD) method could be controlled by the carbon feeding rate at the growth stage. A unified hypothesis on the relationship between nanoparticle size, growth condition, growth temperature, and diameter of the resulting nanotubes was developed and used to explain the relationship. It was shown that the diameters of SWNTs can be controlled even when highly polydisperse nanoparticles were used as catalyst. Such control enabled us to synthesize uniform small-diameter SWNTs at low carbon feeding rates. Additionally, understanding of the important role of the carbon feeding rate can be used to explain the cause of low growth efficiency in most CVD processes. It would also help us to design methods to improve the growth efficiency of CVD growth of nanotubes.     

Study of the quality of carbon nanotubes produced by chemical vapor deposition

Method for obtaining carbon nanotubes by the method of chemical vapor deposition with varied amount of catalyst, reaction duration, and temperature is considered. The synthesis of carbon nanotubes with various mode parameters was experimentally studied. The quality of the carbon nanotubes was examined by Raman spectroscopy. It was found that the defectiveness of the carbon nanotubes depends on the synthesis parameters.     

Combinatorial synthesis of carbon nanotubes by the catalytic chemical vapor deposition method

Summary Bimetallic (Fe-Co) catalyst samples prepared from different precursors over various supports were tested in carbon nanotube (CNT) production. In order to quicken the evaluation of the performance of the catalysts a combinatorial arrangement was used.</o:p>     

Selective chemical vapor deposition synthesis of double-wall carbon nanotubes on mesoporous silica

Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes.     

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.     

Preparation and hydrogen storage properties of an Li-Mg-N-H system

An Li-Mg-N-H system has been synthesized from Mg(NH₂)₂ and LiH in the ratio 3:8 by a ball-milling process and its dehydrogenation/rehydrogenation properties at around 190°C were investigated. XRD, FTIR and TG results showed that the system was composed of an LiH phase and an amorphous Mg(NH₂)₂ phase with a purity of 90%. A reversible hydrogen storage capacity of 4.7% was observed during the first cycle and more than 90% of the stored hydrogen was desorbed within 100 min for each cycle. However, only 4.2% and 2.9%, respectively, of hydrogen was observed during two subsequent dehydrogenation cycles. In situ GC results showed that no NH3 could be observed during the dehydrogenation process. On the basis of the SEM and XRD results, the loss in hydrogen storage capacity can be mainly attributed to agglomeration, oxidation and crystallization of the materials.     

The effect of surface electrolytic treatment on carbon fibers and the microstructure of pyrocarbon around it during chemical vapor deposition

Before chemical vapor deposition, carbon fibers were electrolyzed for different time, using 33 wt% nitric acid and 5 wt% ammonium bicarbonate solution as electrolyte solution respectively. Effects of the electrolytic treatments on the morphology and chemical functional groups of carbon fibers were deeply analyzed. The influence of these surface treatments on the deposition of pyrocarbon during chemical vapor deposition was also investigated. Results show that the electrolytic treatments for proper time improve the surface morphology and adjust the surface functional groups of carbon fibers. The main functional groups on fiber surface are HBS and –COOH groups, which then induce the efficient deposition of pyrocarbon and improve the microstructure of pyrocarbon during chemical vapor deposition.     

Preparation and formation mechanism of CdS nano-films via chemical bath deposition

CdS semiconductor nano-films were grown on ITO glass substrates by means of chemical bath deposition (CBD), with Cd(NO₃)₂ as Cd ion and (NH₂)₂CS as S ion sources. The concentration of Cd ions, deposition temperature, deposition time and post-treatment temperature have an impact on the formation of CdS nano-films. UV-vis absorption spectrum and atomic force microscope (AFM) images indicated that the change of concentration and post-treatment temperature may adjust the band-gap of CdS to obtain stable, homogeneous and compact films. Formation mechanism of the crystal nucleus and CdS film was also discussed. Active sites on the surface of ITO are critical to the formation of the crystal nucleus and a uniform and compact CdS nano-film. The active site and crystal nucleus are formed due to the comprehensive effect of electricity, thermodynamics and chemistry. __________ Translated from Journal of Jilin University (Science Edition), 2007, 45(1): 116–120 [译自: 吉林大学学报(自然科学版)]     

Effect of processing temperature on growing bamboo-like carbon nanotubes by chemical vapor deposition

The present article demonstrates a simple, eco-friendly route for the fabrication of carbon nanotubes (CNTs) with different morphologies, including the fascinating bamboo-like structures without complex catalyst/support preparation procedures. A thermal chemical vapor deposition (CVD) technique that utilized natural pozzolan supports and a solid carbon source, that is, a mixture of camphor and ferrocene in a weight ratio of 20:1, was carried out at different temperatures where the ferrocene played also the role of catalyst. The pozzolan chemical composition and mineral identification were determined by energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The morphology of the fabricated CNTs was studied via scanning and transmission electron microscopies (SEM and TEM). It was revealed that both conventional tubular and bamboo-like nanotubes grow at 750 °C while the bamboo-like morphology prevails at 850 °C. The better nanostructure uniformity at higher deposition temperature was accompanied by an improved nanotube graphitization degree that was verified by Raman spectroscopy. Yet, the reduction of the CNTs production yield was recorded by thermogravimetric analysis (TGA). The experimental data are interpreted and discussed as an interplay between the CNTs processing temperature, morphology and growth mechanism. Thus, the growth of either tubular or bamboo-like nanostructures is suggested to be ruled by the competitive surface and bulk diffusions of carbon onto and into the catalyst surface. The growth depends on the size of catalyst nanoparticles sintered at different temperatures. The favorable role of the pozzolan supporting materials in the formation of bamboo-like tubes is emphasized.     

Monitoring the chemical vapor deposition growth of multiwalled carbon nanotubes by tapered element oscillating microbalance

The growth of multiwalled carbon nanotubes (MWCNTs) produced by a catalytic chemical vapor deposition (CCVD) process has been monitored using a tapered element oscillating microbalance (TEOM) probe. This technique displays a high sensitivity (<1 microg). Growths in the TEOM microreactor are investigated with catalytic particles (Fe, Ni) dispersed on different supports. First, high surface area FeAl2O3 or Fe (Ni) exchanged on zeolite powders is used. Second, growths are performed on array of nickel dots or FeSi-nc particles dispersed on large holes patterned on Si(100) substrates. An accurate monitoring of the early stages of growth permits a precise evaluation of the growth rates and shows substantial differences between these samples which greatly differ by the surface area. On catalysts dispersed on Si(100) the mass uptake is linear throughout the process. On high surface area catalysts, however, a saturation of the mass uptake is indifferently observed. This saturation is explained either by diffusion limitation by the growing MWCNTs or by internal diffusion through the pores or external diffusion through the grains of the catalyst. The kinetic dependence with partial pressure of the incoming C2H6:H2 gas mixture is then explored on the FeAl2O3 catalyst. A linear dependence of the MWCNT growth an (P(C2H6)/P(H2))(1/2) is found. A simple model is then developed that accounts for this dependence only if an associative and competitive adsorption of ethane is the rate determining step of the overall process. These results thus bring insight to improve and control the CCVD growth kinetics of MWCNTs.     

Effect of support and reactant on the yield and structure of carbon growth by chemical vapor deposition

The effect of catalyst support and reactant on the yield and structure of carbon growth has been investigated in the chemical vapor deposition (CVD) process. Powder Fe and Fe/Al(2)O(3) were the catalysts studied, and CO/H(2), CO, CH(4), and C(2)H(6)/H(2) were used as gas precursors. Platelet and fishbone-tubular structures were produced on powder and supported Fe from CO/H(2), with average diameters of 115 and 45 nm and yields of 28.8 and 17.6 g of C/g of cat. in 8.5 h, respectively. Onionlike carbon was the main structure produced from pure CO on both catalysts. In contrast, from hydrocarbons the highest yield of 2.24 g of C/g of cat. was achieved on Fe/Al(2)O(3), with predominantly tubular structures produced and average tube diameters close to 21 nm. It is concluded that the reactivity and carbon nanostructures are dictated by the size and crystallographic orientation of the catalyst particles. It has been suggested that the tubular structures were grown by continuous carbon supply directly to the tube, but the fiber structures were grown in a layer-by-layer manner. Controlled synthesis of carbon nanotube, platelet nanofiber, fishbone-tubular nanofiber, and onionlike carbon with high selectivity and yield was demonstrated.     

Synthesis of helical and straight carbon nanofibers by chemical vapor deposition using alkali chloride catalysts

Microchimica Acta - Carbon nanofibers were synthesized by chemical vapor deposition using alkali chloride catalysts at a temperature range from 500 to 700&nbsp;°C. Depending on the...     

Electrochemical storage of hydrogen in nanocarbon materials: electrochemical characterization of carbon black matrices

In this work, various types of carbon black are electrochemically characterized to study their possible use in the electrochemical evaluation of fullerene materials as hydrogen storage candidates. The cyclic voltammetry and chronopotentiometry studies were performed in alkaline media, 6 M KOH, with carbon paste electrodes. Differences in the electrodes' electrochemical response and their correlation with the various surface chemistries, morphology and doping species of carbon blacks suggest a stronger dependency on the presence of doping agents (foreign metals) and on the surface structure than on the carbon black surface area. The study allows the selection of appropriate carbon black materials to be used as matrixes in future fullerene composite studies. Electronic Publication     

Microstructure and composition of silicon carbide films deposited on carbon fibers by chemical vapor deposition

The microstructure and the composition of CVD silicon carbide films used as fiber coatings in composite materials were investigated by photoelectron spectroscopy and transmission electron microscopy. The films with a uniform thickness of 50 nm consisted of small SiC grains with a mean diameter of 15 nm and showed a stripe contrast in bright field images. Large grains with diameters in the dimension of the film thickness were used for imaging the lattice structure by high-resolution electron microscopy. The results are discussed as a polytype of cubic lamellae of a few nanometers and intermediate random stacking sequences of hexagonal structure. Received: 30 July 1997 / Accepted: 16 December 1997