GCMC simulation of hydrogen physisorption on carbon nanotubes and nanotube arrays

Properties of hydrogen physisorption in single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs) and SWCNT arrays are investigated in detail by grand canonical Monte Carlo simulation. The optimization of hydrogen storage capacity at 298 K and 10 MPa as a function of SWCNT diameter, MWCNT inter-tube spacing, and SWCNT array configuration is discussed.     

Selective oxidation of single-walled carbon nanotubes using carbon dioxide

A simple process for selective removal of carbon from single-walled carbon nanotube samples was developed based on a mild oxidation by carbon dioxide. The reactivity profiles of as prepared and purified nanotube samples were determined using both TG and a related analytical technique, controlled atmosphere programmed temperature oxidation (CAPTO). The complex differential rate curves for weight loss (DTG) or carbon dioxide evolution (CAPTO) could be resolved by a series of Gaussian peaks each associated with carbonaceous species of different reactivity. Comparisons were made between samples as received after preparation by the laser ablation method, after purification by nitric acid oxidation, and both of these after reaction with CO₂. The DTG of as prepared tubes had a broad major peak centered about 410 °C. Mild oxidation of as prepared nanotubes under flowing carbon dioxide at 600 °C preferentially removed more reactive carbon species leaving behind a narrower distribution about the major peak in DTG. In contrast to the as prepared material, the sample that had been purified using nitric acid had a more distinct separation of the major DTG peaks between more and less readily oxidized material. Oxidation of this sample with CO₂ selectively removed the peak associated with the most readily oxidized material. The original CO₂ oxidation experiments performed on the analytical scale were successfully scaled up to a small preparative scale.     

Prediction of elastic properties for single-walled carbon nanotubes

Based on a link between molecular and solid mechanics, an analytical method was developed for modeling the elastic properties of single-walled carbon nanotubes (SWNTs). A SWNT is regarded as a continuum-shell model which is composed of the discrete molecular structures linked by the carbon-to-carbon bonds. The elastic properties were investigated for the SWNTs as a function of the nanotube size in terms of the chiral vector integers (n,m). The theoretical prediction on elastic properties agreed reasonably with the existing experiment and theoretical results. The present formulas are able to serve as a good approximation of the elastic properties for SWNTs.     

Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes

A systematic study was carried out to dope single-walled carbon nanotube (SWNT) bundles with varying amounts of boron using the pulsed laser vaporization technique. Targets containing boron concentrations ranging from 0.5 to 10 at.% boron were prepared by mixing elemental boron with carbon paste and the Co/Ni catalysts. The laser-generated products that were obtained from these targets were characterized by high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), thermoelectric power (TEP) measurements, and Raman scattering experiments. Electron microscopy and Raman studies revealed that the presence of various levels of boron concentration in the target strongly affected the products that were prepared. SWNTs were found in the products prepared from targets containing up through 3 at.% boron, and high resolution EELS estimated that less than 0.05-0.1 at.% boron is present in the SWNT lattice. The absence of SWNT bundles in the products derived from targets containing more than 3 at.% boron implies that the presence of excess boron in the carbon plume severely inhibits the carbon nanotube growth. The overall effect of the boron incorporation primarily leads to: (i) a systematic increase in intensity of the disorder-induced band (D-band) upon boron doping, with increasing D-band intensity observed for higher doping levels, (ii) a systematic downshift in the G′-band frequency due the relatively weaker C-B bond, and (iii) a non-linear variation in the RBM and G′-band intensities which is attributed to shifts in resonance conditions in the doped tubes. Resonant Raman spectroscopy thus provides large changes in the intensity of prominent features even when the dopant concentration is below the detectable limit of EELS (0.05-0.1 at.%). Thermoelectric power data also provide complementary evidence for the presence of a small boron concentration in the SWNT lattice which transforms the SWNTs into a permanently p-type material.     

The role of carbon nanotube structure in purification and hydrogen adsorption

Structural properties of carbon nanotubes were studied by using samples from various manufacturers synthesized by different processes. A two-stage purification method was applied to all samples. Relationships between synthesis techniques and carbon nanotube structure are discussed. The role of carbon nanotube structural features such as degree of crystallinity, tube diameter, tube wall structure, and bundling behavior in purification and hydrogen adsorption were investigated by a combination of transmission electron microscopy and magnetic resonance techniques. It is suggested that MWNTs with low crystallinity and SWNTs with large diameters and open tube ends yielded the highest hydrogen uptake capacities. Both MWNTs and SWNTs show low hydrogen storage capacities (less than 1 wt%) at hydrogen pressures up to 1480 kPa.     

On the control of carbon nanostructures for hydrogen storage applications

The storage of hydrogen in different carbon nanostructures has been investigated using classical Monte-Carlo simulations techniques. Very low hydrogen uptakes (?1% wt) have been calculated for single-walled and double-walled carbon nanotubes, as well as for graphite nanofibers at 293 K and 10 MPa. The amount of hydrogen uptake strongly depends on the porosity within the nanostructure network where optimal arrangements give rise to the formation of a well-defined two-dimensional adsorbed hydrogen layer. The presence of metallic impurities within single-walled nanotube bundles was modeled by disseminating atomic particles, characterized by a highly attractive potential, throughout the nanotube network. It has been found that the presence of metallic particles significantly enhances the hydrogen uptake, but not to a point where this could be considered a promising storage solution.     

Spectroscopic characterization of contaminants and interaction with gases in single-walled carbon nanotubes

Several spectroscopic techniques have been used to investigate the presence of contaminants in a commercial purified single-walled carbon nanotube (SWCNT) bucky paper, to determine their cleaning procedure in ultra-high-vacuum conditions and to study how impurities influence the interaction between SWCNTs and gas phase molecules. Nickel catalyst particles and sodium-containing species, likely a residual of the surfactant bath, were fully removed only after prolonged (>2 h) annealing at 1270 ± 30 K. Other impurity elements (S and Si) remain in the material as localised clusters that do not interact with the SWCNTs and do not interfere with their properties.A dramatic difference was observed when the Na-contaminated or the Na-free nanotubes interacted with molecular oxygen. O₂ adsorption was strongly altered by the Na traces, which simulated an intense sample oxidation causing a modification of the tube electronic properties. On the contrary, for the Na-free sample the lack of adsorbed oxygen and the stability of the C1s core level after large O₂ doses demonstrated the absence of any chemical bond between SWCNTs and O₂. Similarly, exposures to N₂, H₂O and CO do not have influence on the electronic properties of SWCNTs. Instead, a sizeable effect on the electronic spectra was observed for SO₂, NO and NO₂ adsorption. The sensitivity of the SWCNT electronic spectra to ppb quantities of nitrogen oxides and sulfur oxide undoubtedly foresees applications in the field of toxic gas sensing.     

Thionine-mediated chemistry of carbon nanotubes

Thionine can be employed as a kind of useful functional molecule for the non-covalent functionalization of carbon nanotubes, as it shows a strong interaction with either SWNTs or MWNTs. Attachment of thionine molecules onto the sidewalls of carbon nanotubes would improve the solubility and lower the thermal stability of original carbon nanotubes. More importantly, it may functionalize the surface of carbon nanotubes with rich NH₂ groups and therefore open up more opportunities for the surface chemistry of carbon nanotubes. It has been proved that through the modification of small thionine molecules, other kinds of species such as cytochrome C and TiO₂ nanoparticles could be easily and selectively introduced onto the surface of carbon nanotubes. With this approach, SWNTs or MWNTs can be tailored with desired functional structures and properties.     

Covalent functionalization of single-walled carbon nanotubes by aniline electrochemical polymerization

Electrochemical polymerization of aniline in an HCl solution on a single-walled carbon nanotubes (SWNTs) film has been studied by Raman and FTIR spectroscopy. It is shown that this method leads to a covalent functionalization of SWNTs with polyaniline (PANI). A careful study in Raman scattering shows that the increase in the intensity of the band at 178 cm⁻¹ associated with radial breathing modes of SWNTs bundles suggests an additional nanotubes roping with PANI as a binding agent. A post chemical treatment with the NH₄OH solution of polymer-functionalized SWNTs involves an internal redox reaction between PANI and carbon nanotubes. As a result, the polymer chain undergoes a transition from the semi-oxidized state into a reduced one.     

Preparation of short carbon nanotubes by mechanical ball milling and their hydrogen adsorption behavior

Short multi-wall carbon nanotubes (MWNTs) with open tips were obtained by mechanical ball milling. The microstructure characteristics of MWNTs before and after ball milling were checked by transmission electron microscopy (TEM). The effect of ball milling on the hydrogen adsorption behavior of the MWNTs was studied. The hydrogen adsorption experiments were carried out at room temperature under a pressure of 8-9 MPa. The hydrogen adsorption capacity of carbon nanotubes milled for 10 h was 0.66 wt%, which was about six times that of MWNTs without milling. For the carbon nanotubes milled with MgO for 1 h, a hydrogen adsorption capacity of 0.69 wt% was obtained. The enhancement of hydrogen adsorption might result from the increase of defects and surface area of the MWNTs caused by ball milling.     

Observation of single-walled carbon nanotubes by photoemission microscopy

Single-walled carbon nanotube networks grown on SiO₂ pillars were studied by means of scanning photoemission microscopy. The individual nanotubes or nanotube bundles growing from the pillar tops were observed in C 1s images. Band bending near catalytic Fe/nanotube contacts in an end-bonded configuration was studied by measuring C 1s spectra along the tube axes. Within our experimental resolution, no band bending was observed. This implies that the depletion width is less than the spatial resolution of the scanning photoemission microscope (90 nm) or that the amount of the band bending is less than 0.1 eV.     

Functionalization of single-walled carbon nanotubes by using alkyl-halides

In this paper we demonstrate the functionalization of single-walled carbon nanotubes prepared by chemical vapor deposition. The chosen functionalization agents were alkyl-halides such as trifluoromethane (TFM) and trichloromethane (TCM); or double bond containing alkyl-halides as tetrachloroethylene (TCE) and hexafluoropropene (HFP) that can easily form radicals. Functionalization of samples was carried out under mild conditions, by ball milling of nanotubes in an atmosphere of functionalization agent, at room temperature. For the sake of comparison, chlorination was also performed by chlorine gas. In this process the cleavage of nanotube C-C bonds results in active sites, which can activate molecules in gas phase or adsorbed on the surface of carbon nanotubes. Halogenated samples were characterized by means of particle induced γ-ray emission, transmission electron microscopy, thermogravimetry, and X-ray photoelectron spectroscopy. We concluded that this method gives functionalized single-walled carbon nanotubes in the range of 0.3-3.5 wt.% of fluorine and 5.5-17.5 wt.% of chlorine.     

Electrochemical storage of energy in carbon nanotubes and nanostructured carbons

Possibilities of electrochemical energy conversion using carbon nanotubes and related materials in various systems, such as lithium batteries, supercapacitors, hydrogen storage, are considered. It is shown that for these applications the electrochemical properties of multiwalled (MWNTs) and single walled (SWNTs) nanotubes are essentially dominated by their mesoporous character. During lithium insertion into nanotubular materials a high irreversible capacity C_irr (from 460 to 1080 mAh/g) has been observed after the first cycle with a tendency to further decomposition of electrolyte with cycling. Penetration of solvated lithium ions in the accessible mesopores is at the origin of this phenomenon; an almost linear dependence has been found between the mesopore volume and C_irr. Reversible capacity for lithium insertion C_rev ranged between 220 and 780 mAh/g; however, a great divergence (hysteresis) between insertion and extraction characteristics was observed independently on the kind of nanotubes and oxygen content. Amount of lithium stored by electrostatic attraction is negligible in comparison to real redox reactions which for thermodynamic reasons present linear variation of potential, especially during deinsertion (pseudocapacitive effects). During positive polarization, i.e., removal of lithium, resistivity of the electrode also gradually increases. Due to the open network of mesopores formed by the nanotubes entanglement, and consequently an easily accessible electrode-electrolyte interface, nanotubular materials are quite adapted for supercapacitor electrodes in various electrolytic solutions. High values of capacitance (80 F/g) have been obtained in 6 M KOH for materials with a surface area of only ca. 430 m²/g. Capacitance values have been enhanced either by additional oxygenated functionalisation of nanotubes (130 F/g) or by conducting polypyrrole (PPy) electrodeposition where the maximum values reached 170 F/g. The next domain of energy storage in the carbon nanostructures is the accumulation of hydrogen by the electrochemical decomposition of aqueous alkaline medium on a negatively polarized carbon electrode in ambient conditions. For SWNTs only moderate values (below 0.5 wt.% of H₂) have been found, while for activated carbons with highly developed surface area of 1500 m²/g, the amount of reversibly sorbed hydrogen was ca. 2 wt.%, noticeably larger than under dihydrogen pressure (only 0.4 wt.% for the same material at 70 bar and 273 K). The enhancement observed for the activated carbon is interpreted by the formation of nascent hydrogen during water reduction which penetrates easily in the available carbon nanopores. The values obtained by this method are comparable to those of metallic alloys, such as LaNi₅ for example.