Hydrogen storage in carbon nanotubes.

The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor.

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Purification process for vertically aligned carbon nanofibers.

Individual, free-standing, vertically aligned multiwall carbon nanotubes or nanofibers are ideal for sensor and electrode applications. Our plasma-enhanced chemical vapor deposition techniques for producing free-standing and vertically aligned carbon nanofibers use catalyst particles at the tip of the fiber. Here we present a simple purification process for the removal of iron catalyst particles at the tip of vertically aligned carbon nanofibers derived by plasma-enhanced chemical vapor deposition. The first step involves thermal oxidation in air, at temperatures of 200-400 degrees C, resulting in the physical swelling of the iron particles from the formation of iron oxide. Subsequently, the complete removal of the iron oxide particles is achieved with diluted acid (12% HCl). The purification process appears to be very efficient at removing all of the iron catalyst particles. Electron microscopy images and Raman spectroscopy data indicate that the purification process does not damage the graphitic structure of the nanotubes.

Synthesis and thermoelectric power of nitrogen-doped carbon nanotubes.

We have previously shown that high-purity multiwalled carbon nanotubes (pristine MWNTs) can be prepared from a mixture of xylene-ferrocene (99 at% C:1 at% Fe) inside a quartz tube reactor operating at approximately 700 degrees C. In a similar process, approximately 3 g of melamine (C3H6N6) was introduced during the growth of MWNTs to prepare nitrogen-doped nanotubes. The structural and electronic properties of nitrogen-doped MWNTs were determined by scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and thermopower measurements. The individual nitrogen-doped nanotube exhibits a bamboo-like structure and comprises 6-16 tube walls, as evidenced by HRTEM studies. The EELS measurements yielded an average nitrogen content of approximately 5 at% in the doped tubes. The thermoelectric power data of nitrogen-doped MWNTs remained negative even after exposure to oxygen for an extended period of time, suggesting that nitrogen doping of MWNTs renders them n-type, consistent with scanning tunneling spectroscopic studies on similar nanotubes.

Mesoporous silicates as nanoreactors for carbon nanotube production in the absence of transition metal catalysts.

Carbon nanotubes were produced from either a template or the polymer-filled pore systems of mesoporous silicates of various structures and dimensions by heat treatment in the absence of air. Successful synthesis was done when the template molecules contained little or no oxygen. For SBA-15 material, where the structure-directing molecule used for synthesis of mesoporous silicate was polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, no carbon nanostructures were formed. A peculiar carbon nanostructure was generated from the template for pore expanded MCM-41. To demonstrate carbon nanotube formation from polymer in the mesoporous silicates, the mesopores of MCM-41, MCM-48, and SBA-15 silicates were filled with divinyl-benzene polymer and then graphitized at 1300 K. The polymer was successfully transformed into carbon nanotubes for the MCM class silicate but not the SBA-15 silicate.

High-pressure Raman study of debundled single-walled carbon nanotubes.

We report the pressure dependence for the radial (omega R) and tangential (omega T) band frequencies in debundled single-walled carbon nanotubes (SWNTs) derived from laser-synthesized SWNT bundles. As previously described, a chemical procedure was used to prepare debundled SWNTs from as-prepared, large SWNT bundles. The normalized pressure coefficient for omega R in the debundled sample was compared with the corresponding value in the bundled sample to quantify the strength of van der Waals interactions between tubes in these nanotube materials. Furthermore, the pressure dependences for the radial (omega R) and tangential (omega T) band frequencies in debundled tubes were also compared with corresponding dependences predicted for isolated SWNTs, obtained with generalized tight binding molecular dynamic (GTBMD) simulations described in our previous work. The results presented here collectively suggest that the van der Waals interaction is still strong in the debundled sample studied here, which contained predominantly small bundles of SWNTs rather than isolated tubes.

Production and characterization of polymer nanocomposites with highly aligned single-walled carbon nanotubes.

We report the production and characterization of polymer nanocomposites with single-walled carbon nanotubes having improved mechanical properties and exceptional nanotube alignment. High-pressure carbon monoxide nanotubes (HiPco) were efficiently distributed in polystyrene (PS) and polyethylene (PE) with a twin-screw compounder. Nanotube concentrations were 1, 5, 10, and 20 wt% in PE composites and 0.7 wt% in PS composites. PE composites were melt-spun into fibers to achieve highly aligned nanotubes. Polarized Raman spectroscopy shows that the degree of alignment increases with decreasing fiber diameter and decreases with increasing nanotube loading. The orientation distribution function of a 1 wt% HiPco/PE composite had a full width at half-maximum of approximately 5 degrees. The elastic modulus increases up to 450% relative to PE fibers for 20 wt% nanotube loading at an intermediate fiber diameter of 100 microns.

Recent advances in the preparation and utilization of carbon nanotubes for hydrogen storage.

Recent progress in the production, purification, and experimental and theoretical investigations of carbon nanotubes for hydrogen storage are reviewed. From the industrial point of view, the chemical vapor deposition process has shown advantages over laser ablation and electric-arc-discharge methods. The ultimate goal in nanotube synthesis should be to gain control over geometrical aspects of nanotubes, such as location and orientation, and the atomic structure of nanotubes, including helicity and diameter. There is currently no effective and simple purification procedure that fulfills all requirements for processing carbon nanotubes. Purification is still the bottleneck for technical applications, especially where large amounts of material are required. Although the alkalimetal-doped carbon nanotubes showed high H2 weight uptake, further investigations indicated that some of this uptake was due to water rather than hydrogen. This discovery indicates a potential source of error in evaluation of the storage capacity of doped carbon nanotubes. Nevertheless, currently available single-wall nanotubes yield a hydrogen uptake value near 4 wt% under moderate pressure and room temperature. A further 50% increase is needed to meet U.S. Department of Energy targets for commercial exploitation. Meeting this target will require combining experimental and theoretical efforts to achieve a full understanding of the adsorption process, so that the uptake can be rationally optimized to commercially attractive levels. Large-scale production and purification of carbon nanotubes and remarkable improvement of H2 storage capacity in carbon nanotubes represent significant technological and theoretical challenges in the years to come.

Carbon nanotube-magnesium oxide cube networks.

For future applications based on carbon nanotubes, two- and three-dimensional architectures of nanotubes need to be assembled. In many cases this will involve the creation of nanotube units and nodes from which these nanotubes can be distributed in a network. We demonstrate that this idea is plausible by using a template of the correct dimensions and shape, and that has facets that provide the right growth conditions: submicrometer-sized MgO cubes are used to grow nanotubes by chemical vapor deposition. The resulting networks often show that the MgO cubes function as distribution sites for arrays of aligned nanotubes.

Structural characterization of nanotube fibers by x-ray scattering.

Nanotube fibers with diameters ranging between 10 and 100 microns were produced by a simple spinning process. These fibers were studied by x-ray scattering--a technique that allows good visualization of the composition as well as the alignment of the constituents. The fibers were found to be composed of bundles of single wall carbon nanotubes, poly(vinyl alcohol) polymer chains, graphitic objects, and Ni-based particles. The nanotubes and poly(vinyl alcohol) chains were preferentially oriented along the fiber axis.

Single-wall carbon nanotubes under high pressures to 62 GPa studied using designer diamond anvils.

Single-wall carbon nanotube samples were studied under high pressures to 62 GPa using designer diamond anvils with buried electrical microprobes that allowed for monitoring of the four-probe electrical resistance at elevated pressure. After initial densification, the electrical resistance shows a steady increase from 3 to 42 GPa, followed by a sharp rise above 42 GPa. This sharp rise in electrical resistance at high pressures is attributed to opening of an energy band gap with compression. Nanoindentation hardness measurements on the pressure-treated carbon nanotube samples gave a hardness value of 0.50 +/- 0.03 GPa. This hardness value is approximately 2 orders of magnitude lower than the amorphous carbon phase produced in fullerenes under similar conditions. Therefore, the pressure treatment of single-wall carbon nanotubes to 62 GPa did not produce a superhard carbon phase.

Nuclear magnetic resonance of molecular hydrogen trapped in single-walled carbon nanotube bundles.

Molecular dynamics of hydrogen trapped in single-walled carbon nanotube bundles was analyzed by nuclear magnetic resonance. The chemical shift of hydrogen was about 5.1 ppm at 293 K, which is similar to that of water. The relaxation time, T1, was about 0.1-0.2 s. Values in this work are comparable to those for hydrogen loaded in silica and a-Si.

High yield of pure multiwalled carbon nanotubes from the catalytic decomposition of acetylene on in-situ formed cobalt nanoparticles.

For the first time, multiwalled carbon nanotubes (MWNTs) could be formed selectively in a high yield, free of any disordered carbon by-product, from the catalytic decomposition of acetylene at 600 degrees C on a CoxMg(1-x)O solid solution. Starting from 1 g of catalytic substrate, 4 g of pure MWNTs were obtained after its dissolution in boiling concentrated HCl, without any additional purification in strongly oxidizing medium, as is required for other methods of nanotube production. In situ reduction of CoO by dihydrogen liberated from acetylene decomposition allows highly divided metal particles to be continuously produced as synthesis proceeds. This is undoubtedly the reason for the good performance of the catalyst and for the ability to produce nanotubes in a narrow diameter range, namely from 10 to 15 nm. With the use of acetylene instead of methane, the synthesis proceeds at low temperature, which prevents the growth of carbon shells, in which the metal particles are generally embedded, decreasing their activity. Because of the very low specific surface area of the catalyst support, the amount of disordered carbon by-product formed is negligible.

Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates.

An ethylene-air laminar diffusion flame successfully provided silicon substrates of anodic aluminum oxide (AAO) template with vertically oriented well-aligned carbon nanotubes. Field emission scanning electron microscopy (SEM) showed that open-tipped carbon nanotubes consisting of tube elements with the same length and diameter uniformly coated the template. High-resolution transmission electron microscopy (TEM) analyses revealed these nanotubes to be multiwalled carbon nanotubes, some well graphitized. It was found that cobalt catalyst particles, but not the porous aluminum templates, helped the growth of carbon nanotubes through graphitization and bonding of carbon nanotubes to the silicon substrates.

A perfect carbon nanotube with two closed ends.

A perfect carbon nanotube with two closed ends consisting of graphitized carbon was experimentally observed. The large carbon nanotube, with a diameter of 187 nm and a length of 1.2 microns, was synthesized by pyrolysis of iron(II) phthalocyanine (FePc) under an Ar/NH3 flow at 900 degrees C on a nickel substrate. The structure and composition of the nanotube were determined by high-resolution transmission electron microscopy and electron energy loss spectroscopy. The carbon nanotube seems to grow spontaneously by some autocatalytic process.

Synthesis and characterization of lanthanum carbide nanotubes.

Lanthanum carbide nanotubes have been synthesized by d.c. arc evaporation (approximately 20-30 V, approximately 200 Amp) of lanthanum metal (90 wt.%)-loaded graphite rod in a helium atmosphere (665 mbar). To explore the possibility of formation of lanthanum carbide nanotubes, the experiments were carried out with lanthanum metal in different concentrations (i.e., 30, 50, 70, and 90 wt.%) in the graphite rod. The as-synthesized samples were characterized by transmission electron microscopy and X-ray diffractometry. Lanthanum carbide nanotubes (LCNTs) with a diameter of approximately 65 to 95 nm and a length of approximately 0.2 to 1.5 microns were obtained in this study.

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide.

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Carbon arc plasma as a source of nanotubes: emission spectroscopy and formation mechanism.

Diagnostics of carbon arc plasma by optical emission spectroscopy during the synthesis of carbon nanotubes is reviewed. Spatial distributions of temperature and C2 radicals in different plasmas are presented. The influence of gas pressure, anode composition, and reaction environment is discussed. Mechanisms of carbon nanotube formation are reviewed, with an emphasis on surface diffusion processes and catalytic effects.

Low-temperature synthesis of large-area CNx nanotube arrays.

Well-aligned nitrogen-doped multiwall carbon nanotube arrays have been successfully grown over large areas on quartz and silicon wafers by floating-catalyst chemical vapor deposition at low temperatures (600 degrees C). These nitrogen-including nanotubes, derived from pyridine-ferrocene mixtures, have smaller outer diameters but larger inner diameters compared with carbon nanotubes grown from a xylene-ferrocene mixture under similar conditions. The N-doped nanotubes exhibit bamboo-like structures in the core. Elemental analysis and electron energy loss spectroscopy analysis show that the as-prepared nanotubes contain as much as 2.62 wt.% N, with most of the N concentrated in the inner few shells of the nanotube. Such large-scale arrays of well-aligned N-doped nanotubes on silicon wafers have a current density as high as 23.8 mA/cm2 at an applied electric field of 17 V/micron, which can be further improved by patterning the tubes and coating the silicon substrate with a conductive thin metal film for the fabrication of flat panel displays.

Spectroscopic probing of organic molecules encapsulated in functionalized carbon nanotubes in solution.

Pyrene was introduced into cavities in functionalized single-walled and multiple-walled carbon nanotubes to be used as a molecular probe in the study of encapsulation. The solubility of these materials in common organic solvents allowed solution-phase absorption and emission spectroscopic measurements. The results, which are consistent with the formation of pyrene excimer, are explained in terms of high local pyrene concentrations and perhaps pyrene microcrystals inside the carbon nanotube cavities. The fluorescence decay results show that there is significant quenching of pyrene excited states by the hosting carbon nanotubes.