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Covalent derivatization of the acidic functional groups in oxidized graphite with octadecylamine renders graphite soluble in common organic solvents. Atomic force microscopic characterization of the soluble species supports the idea that the solutions consist of single and few layer graphene sheets, and we report the first solution properties of graphite.
A newly designed Gemini-shaped hexabenzocoronene amphiphile (1), carrying an isothiouronium ion-appended side chain, self-assembles in CH2Cl2 to form a nanotubular object, whose graphitic wall is densely covered by a positively charged molecular layer of isothiouronium ion pendants. The graphitic nanotube can be dispersed uniformly in aqueous media owing to effective hydration as well as electrostatic repulsion. Post-supramolecular functionalization of the nanotube surface is possible, without disruption of the tubular morphology, by taking advantage of a specific interaction of the isothiouronium ion pendants with oxoanion guests. Mixing with sodium poly(4-styrenesulfonate) results in wrapping of the nanotube, while complexation with an electron-accepting oxoanion such as anthraquinone carboxylate allows photoinduced electron transfer from the graphitic wall to the bound guest molecules.
Branched hydrocarbon propellers (9 and 12) were prepared by stepwise palladium-catalyzed Hagihara-Sonogashira coupling reactions and Diels-Alder cycloadditions and submitted to oxidative cyclodehydrogenation by FeCl3 to afford two new giant graphite disks 2 and 3 with 3-fold symmetry in high yield. One of the precursors, the polyphenylene dendrimer 9 containing 150 carbon atoms, was crystallographically characterized. The poorly soluble graphite disks were characterized by isotope-resolved MALDI-TOF mass spectroscopy, and their electronic and vibrational properties were investigated by solid-state UV-vis and Raman spectroscopy. The effect of molecular size and geometry on their properties was discussed. The molecule 2 represents the largest, 3-fold-symmetric all-benzenoid graphite disk, and the five-membered rings in molecule 3 open the opportunity to synthesize large bowl-shaped PAHs.
In the present paper, the theoretical approach developed in paper 1 is applied to an NH(3) molecule adsorbed on a graphite substrate. The potential energy surfaces (PESs) for the interaction between the molecule and the graphite crystal are described in detail. The molecule exhibits two quasi-equivalent angular position minima of energy ("up" and "down") along the perpendicular axis to the surface. The PES calculations also indicate that the NH(3) molecule has a rotational motion that is moderately hindered, with an energy barrier value of about 14 meV and also a quasi-free lateral translational motion above the surface, indicating a weak corrugation of the graphite (0001) surface. The isosteric heat of adsorption is calculated and is in agreement with the experimental one. Finally, the infrared absorption spectra for the vibrational mode frequency regions are obtained.
Self-assembled monolayers of chrysene and indene on graphite have been observed and characterized individually with scanning tunneling microscopy (STM) at 80 K under low-temperature, ultrahigh vacuum conditions. These molecules are small, polycyclic aromatic hydrocarbons (PAHs) containing no alkyl chains or functional groups that are known to promote two-dimensional self-assembly. Energy minimization and molecular dynamics simulations performed for small groups of the molecules physisorbed on graphite provide insight into the monolayer structure and forces that drive the self-assembly. The adsorption energy for a single chrysene molecule on a model graphite substrate is calculated to be 32 kcal/mol, while that for indene is 17 kcal/mol. Two distinct monolayer structures have been observed for chrysene, corresponding to high- and low-density assemblies. High-resolution STM images taken of chrysene with different bias polarities reveal distinct nodal structure that is characteristic of the molecular electronic state(s) mediating the tunneling process. Density functional theory calculations are utilized in the assignment of the observed electronic states and possible tunneling mechanism. These results are discussed within the context of PAH and soot particle formation, because both chrysene and indene are known reaction products from the combustion of small hydrocarbons. They are also of fundamental interest in the fields of nanotechnology and molecular electronics.
In this study, ordered macroporous carbon with a three-dimensional (3D) interconnected pore structure and a graphitic pore wall was prepared by chemical vapor deposition (CVD) of benzene using inverse silica opal as the template. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectrometry, nitrogen adsorption, and thermogravimetric analysis techniques were used to characterize the carbon samples. The electrochemical properties of the carbon materials as a carbon-based anode for lithium-ion batteries and as a Pt catalyst support for room-temperature methanol electrochemical oxidation were examined. It was observed that the CVD method is a simple route to fabrication of desired carbon nanostructures, affording a carbon with graphitic pore walls and uniform pores. The graphitic nature of the carbon enhances the rate performance and cyclability in lithium-ion batteries. The specific capacity was found to be further improved when SnO(2) nanoparticles were supported on the carbon. The specific activity of Pt catalyst supported on the carbon materials for room-temperature methanol electrochemical oxidation was observed to be higher than that of a commercial Pt catalyst (E-TEK).
In this paper, we present results from molecular dynamic simulations devoted to the characterization of the interaction between water molecules and hydroxylated graphite surfaces considered as models for surfaces of soot emitted by aircraft. The hydroxylated graphite surfaces are modeled by anchoring several OH groups on an infinite graphite plane. The molecular dynamics simulations are based on a classical potential issued from quantum chemical calculations. They are performed at three temperatures (100, 200, and 250 K) to provide a view of the structure and dynamics of water clusters on the model soot surface. These simulations show that the water-OH sites interaction is quite weak compared to the water-water interaction. This leads to the clustering of the water molecules above the surface, and the corresponding water aggregate can only be trapped by the OH sites when the temperature is sufficiently low, or when the density of OH sites is sufficiently high.
The use of carbon nanomaterials in various applications requires precise control of their surface and bulk properties. In this paper, we present a strategy for modifying the surface chemistry, wettability, and electrical conductivity of carbon tubes and films through annealing in a vacuum. Experiments were conducted with 60-300 nm nanotubes (nanopipes), produced by noncatalytic chemical vapor deposition (CVD) in a porous alumina template, and with thin films deposited by the same technique on a glassy carbon substrate having the same structure and chemistry of the CNTs. The surface of the as-produced CVD-carbon, treated with sodium hydroxide to remove the alumina template, is hydrophilic, and the bulk electrical conductivity is lower by a factor of 20 than that of fully graphitic multiwalled nanotubes (MWNT) or bulk graphite. The bulk electrical conductivity increases to the conductivity of graphite after annealing at 2000 degrees C in a high vacuum. The analysis of CNTs by transmission electron microscopy (TEM) and Raman spectroscopy shows the ordering of carbon accompanied by an exponential increase of the in-plane crystallite size, L(a), with increasing annealing temperature. Environmental scanning electron microscopy (ESEM) was used to study the interaction of CNT with water, and contact angle measurements performed using the sessile drop method on CVD-carbon films demonstrate that the contact angle increases nearly linearly with increasing annealing temperature.
An approach for the fabrication of metal nanowires is presented. Palladium wires with diameters less than 50 nm were produced by electrochemical decoration of step edge sites on the surface of highly ordered pyrolytic graphite via the following three steps. First an electrochemical activation step was used to oxidize the edge plane sites on highly ordered pyrolytic graphite surfaces in 0.5 M Na(2)SO(4). Second, a potential cycling step in a 1 mM PdCl(2) solution in 0.1 M H(2)SO(4) was used to form palladium oxide (s) and/or complexes of Pd on the step edges. Third, Pd nanowires were formed by electroreduction after transfer of the graphite to 0.1 M H(2)SO(4). The resulting wires showed a high degree of uniformity. A merit of this approach is that it allowed metal nanowires to be fabricated without the simultaneous formation of nanoparticles on the basal plane terraces, in contrast to other studies of this type. The mesoscopic palladium wires are shown to be useful for the electrochemical sensing of hydrazine.
The stability at elevated temperatures of a solid electrolyte interphase (SEI) formed on a graphite negative electrode in lithium ion batteries was investigated by storage tests and in situ atomic force microscopy (AFM) observation. When the fully discharged graphite electrode was stored at elevated temperatures, the irreversible capacity in the following cycle increased remarkably. On the other hand, when the electrode was stored at the fully charged state at elevated temperatures, it was severely self-discharged during storage. AFM observation of the SEI layer formed on a model electrode of highly oriented pyrolytic graphite revealed two important facts on the stability of the SEI at elevated temperatures: (i) dissolution and agglomeration of the SEI layer at the discharged state and (ii) serious SEI growth at the charged state. These phenomena well explain the results of the charge and discharge tests. It was also shown that the addition of vinylene carbonate greatly improves the stability of the SEI at elevated temperatures, and gives good charge and discharge performance after storage.
Self-assembled monolayers of carboxylic esters (stearic acid palmityl ester, lauric acid palmityl ester, and lauric acid behenyl ester) on graphite were investigated using scanning tunneling microscopy. All three esters, which are bent at the carboxylic group in the gas phase, are distorted into a straight-chain shape upon self-assembly on graphite. This results from optimizing the adsorption energy by matching the adsorbate molecular chain with the graphite substrate lattice periodicity. In all the formed lamellae, the long alkyl chain of the ester always aligns with the long chain of the adjacent molecule. Steric repulsion of the carbonyl group pointing perpendicularly to the neighboring molecule weakens the interaction of the ester molecule with the substrate. The ester molecules then easily self-assemble into multilamellae with molecular chain-trough angles of 73, 61, and 49 degrees in addition to the 90 degrees angle typical of n-alkane monolayers. This results from a shifting of 1/2, 1, or 3/2 units from the adjacent molecule in a lamella. The relatively weak interaction between ester molecules and substrate lattice also results in the formation of zigzag patterns with domain-domain angles of 145, 133, and 122 degrees , respectively. The structures of esters adsorbed on HOPG indicate, contrary to what might be expected, that physisorbed molecular adsorbates do not necessarily have the same geometry as in the gas phase.
Adsorption of ethylene and ethane on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers is studied in detail to investigate the packing efficiency, the two-dimensional critical temperature, and the variation of the isosteric heat of adsorption with loading and temperature. Here we used a Monte Carlo simulation method with a grand canonical Monte Carlo ensemble. A number of two-center Lennard-Jones (LJ) potential models are investigated to study the impact of the choice of potential models in the description of adsorption behavior. We chose two 2C-LJ potential models in our investigation of the (i) UA-TraPPE-LJ model of Martin and Siepmann for ethane and Wick et al. for ethylene and (ii) AUA4-LJ model of Ungerer et al. for ethane and Bourasseau et al. for ethylene. These models are used to study the adsorption of ethane and ethylene on graphitized thermal carbon black. It is found that the solid-fluid binary interaction parameter is a function of adsorbate and temperature, and the adsorption isotherms and heat of adsorption are well described by both the UA-TraPPE and AUA models, although the UA-TraPPE model performs slightly better. However, the local distributions predicted by these two models are slightly different. These two models are used to explore the two-dimensional condensation for the graphitized thermal carbon black, and these values are 110 K for ethylene and 120 K for ethane.
In this paper, we studied vapor-liquid equilibria (VLE) and adsorption of ethylene on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers. Simple models of a one-center Lennard-Jones (LJ) potential and a two-center united atom (UA)-LJ potential are investigated to study the impact of the choice of potential models in the description of VLE and adsorption behavior. Here, we used a Monte Carlo simulation method with grand canonical Monte Carlo (GCMC) and Gibbs ensemble Monte Carlo ensembles. The one-center potential model cannot describe adequately the VLE over the practical range of temperature from the triple point to the critical point. On the other hand, the two-center potential model (Wick et al. J. Phys. Chem. B 2000, 104, 8008-8016) performs well in the description of VLE (saturated vapor and liquid densities and vapor pressure) over the wide range of temperature. This UA-LJ model is then used in the study of adsorption of ethylene on graphitized thermal carbon black and in slit pores. Agreement between the GCMC simulation results and the experimental data on graphitized thermal carbon black for moderate temperatures is excellent, demonstrating that the potential of the GCMC method and the proper choice of potential model are essential to investigate adsorption. For slit pores of various sizes, we have found that the behavior of ethylene exhibits a number of features that are not manifested in the study of spherical LJ particles. In particular, the singlet density distribution versus distance across the pore and the angle between the molecular axis and the z direction provide rich information about the way molecules arrange themselves when the pore width is varied. Such an arrangement has been found to be very sensitive to the pore width.
Grand canonical Monte Carlo (GCMC) simulation was used for the systematic investigation of the supercritical methane adsorption at 273 K on an open graphite surface and in slit-like micropores of different sizes. For both considered adsorption systems the calculated excess adsorption isotherms exhibit a maximum. The effect of the pore size on the maximum surface excess and isosteric enthalpy of adsorption for methane storage at 273 K is discussed. The microscopic detailed picture of methane densification near the homogeneous graphite wall and in slit-like pores at 273 K is presented with selected local density profiles and snapshots. Finally, the reliable pore size distributions, obtained in the range of the microporosity, for two pitch-based microporous activated carbon fibers are calculated from the local excess adsorption isotherms obtained via the GCMC simulation. The current systematic study of supercritical methane adsorption both on an open graphite surface and in slit-like micropores performed by the GCMC summarizes recent investigations performed at slightly different temperatures and usually a lower pressure range by advanced methods based on the statistical thermodynamics.
High-resolution ellipsometry and neutron diffraction measurements have been used to investigate the structure, growth, and wetting behavior of fluid pentane (n-C(5)H(12)) films adsorbed on graphite substrates. We present isotherms of the thickness of pentane films adsorbed on the basal-plane surfaces of a pyrolytic graphite substrate as a function of the vapor pressure. These isotherms are measured ellipsometrically for temperatures between 130 and 190 K. We also describe neutron diffraction measurements in the temperature range 11-140 K on a deuterated pentane (n-C(5)D(12)) monolayer adsorbed on an exfoliated graphite substrate. Below a temperature of 99 K, the diffraction patterns are consistent with a rectangular centered structure. Above the pentane triple point at 143.5 K, the ellipsometric measurements indicate layer-by-layer adsorption of at least seven fluid pentane layers, each having the same optical thickness. Analysis of the neutron diffraction pattern of a pentane monolayer at a temperature of 130 K is consistent with small clusters having a rectangular-centered structure and an area per molecule of approximately 37 A(2) in coexistence with a fluid monolayer phase. Assuming values of the polarizability tensor from the literature and that the monolayer fluid has the same areal density as that inferred for the coexisting clusters, we calculate an optical thickness of the fluid pentane layers in reasonable agreement with that measured by ellipsometry. We discuss how these results support the previously proposed "footprint reduction" mechanism of alkane monolayer melting. In the hypercritical regime, we show that the layering behavior is consistent with the two-dimensional Ising model and determine the critical temperatures for layers n = 2-5.
The performance of intermolecular potential models on the adsorption of benzene on graphitized thermal carbon black at various temperatures is investigated. Two models contain only dispersive sites, whereas the other two models account explicitly for the dispersive and electrostatic sites. Using numerous data in the literature on benzene adsorption on graphitized thermal carbon black at various temperatures, we have found that the effect of surface mediation on interaction between adsorbed benzene molecules must be accounted for to describe correctly the adsorption isotherm as well as the isosteric heat. Among the two models with partial charges tested, the WSKS model of Wick et al. that has only six dispersive sites and three discrete partial charges is better than the very expensive all-atom model of Jorgensen and Severance. Adsorbed benzene molecules on graphitized thermal carbon black have a complex orientation with respect to distance from the surface and also with respect to loading. At low loadings, they adopt the parallel configuration relative to the graphene surface, whereas at higher loadings (still less than monolayer coverage) some molecules adopt a slant orientation to maximize the fluid-fluid interaction. For loadings in the multilayer region, the orientation of molecules in the first layer is influenced by the presence of molecules in the second layer. The data that are used in this article come from the work of Isirikyan and Kiselev, Pierotti and Smallwood, Pierce and Ewing, Belyakova, Kiselev, and Kovaleva, and Carrott et al.
We present findings on the structure, energies and behaviour of defects in irradiated graphitic carbon materials. Defect production due to high-energy nuclear radiations experienced in graphite moderators is generally associated with undesirable changes in internal energy, microstructure and physical properties--the so-called Wigner effect. On the flip side, the controlled introduction and ability to handle such defects in the electron beam is considered a desirable way to engineer the properties of carbon nanostructures. In both cases, the atomic-level details of structure and interaction are only just beginning to be understood. Here, using a model system of crystalline graphite, we show from first-principles calculations, new details in the behaviour of vacancy and interstitial defects. We identify a prominent barrier-state to energy release, reveal a surprising ability of vacancy defects to bridge the widely spaced atomic layers, and discuss physical property and microstructure changes during irradiation, including interactions with dislocations.
The solvation parameter model is used to study the retention mechanism of neutral organic compounds on porous graphitic carbon with methanol-water mobile phases containing from 0-100% (v/v) methanol. The dominant contribution to retention is the cavity formation-dispersion interaction term, composed of favorable interactions in the mobile phase (hydrophobic effect) and additional contributions from adsorption on the graphite surface. Electron lone pair and dipole-type interactions in the adsorbed state result in increased retention. Hydrogen-bonding interactions are more favorable in the mobile phase resulting in lower retention. The changes in the system constants of the solvation parameter model for cavity formation-dispersion interactions and hydrogen-bond interactions are linearly related to the volume fraction of water in the mobile phase. The system constants for electron lone pair interactions and dipole-type interactions are non-linear and go through a maximum and minimum value, respectively, at a specific mobile phase composition. The solvation parameter model poorly predicts the retention properties of angular molecules. This is probably due to the failure of the characteristic volume to correctly model the contact surface area for the interaction of angular molecules with the planar graphite surface. General factors affecting the quality of model fits for adsorbents are discussed.