The closed-edge structure of graphite and the effect of electrostatic charging.

The properties of graphite, and of few-layer graphene, can be strongly influenced by the edge structure of the graphene planes, but there is still much that we do not understand about the geometry and stability of these edges. We present an experimental and theoretical study of the closed edges of graphite crystals, and of the effect of an electric field on their structure. High-resolution transmission electron microscopy is used to image the edge structure of fresh graphite and of graphite that has been exposed to an electric field, which experiences a separation of the graphene layers. Computer simulations based on density functional theory are used to rationalise and quantify the preference for the formation of multiple concentric loops at the edges. A model is also presented to explain how the application of an electric field leads to the separation of the folded edges.

Microscopy and literature.

This article draws attention to literary works which have been influenced by microscopy, or in which microscopy has played a significant role. The work of writers including Jonathan Swift, Voltaire, George Eliot, H. G. Wells and D. H. Lawrence is discussed. In many cases these authors had direct experience of operating microscopes and viewing the wonders of the microscopic world. However, with the increasing separation of the two cultures, recent examples of microscopy in literature are rare.

The structure of junctions between carbon nanotubes and graphene shells.

Junctions between carbon nanotubes and flat or curved graphene structures are fascinating for a number of reasons. It has been suggested that such junctions could be used in nanoelectronic devices, or as the basis of three-dimensional carbon materials, with many potential applications. However, there have been few detailed experimental analyses of nanotube-graphene connections. Here we describe junctions between nanotubes and graphene shells in a material produced by passing a current through graphite. Transmission electron micrographs show that the junction angles are not random but fall close to multiples of 30°. We show that connections with these angles are the only ones which are consistent with the symmetry of the hexagonal lattice, and molecular models show that a continuous lattice requires the presence of large carbon rings at the junction. Some of the configurations we propose have not been previously considered, and could be used to construct new kinds of three-dimensional carbon architecture. We also discuss the possible formation mechanism of the junctions.

To what extent can mutual shifting of folded carbonaceous walls in slit-like pores affect their adsorption properties?

We have performed systematic Monte Carlo studies on the influence of shifting the walls in slit-like systems constructed from folded graphene sheets on their adsorption properties. Specifically, we have analysed the effect on the mechanism of argon adsorption (T = 87 K) and on adsorption and separation of three binary gas mixtures: CO2/N2, CO2/CH4 and CH4/N2 (T = 298 K). The effects of the changes in interlayer distance were also determined. We show that folding of the walls significantly improves the adsorption and separation properties in comparison to ideal slit-like systems. Moreover, we demonstrate that mutual shift of sheets (for small interlayer distances) causes the appearance of small pores between opposite bulges. This causes an increase in vapour adsorption at low pressures. Due to overlapping of interactions with opposite walls causing an increase in adsorption energy, the mutual shift of sheets is also connected with the rise in efficiency of mixture separation. The effects connected with sheet orientation vanish as the interlayer distance increases.

Folding of graphene slit like pore walls--a simple method of improving CO2 separation from mixtures with CH4 or N2.

We report for the first time a detailed procedure for creating a simulation model of energetically stable, folded graphene-like pores and simulation results of CO2/CH4 and CO2/N2 separation using these structures. We show that folding of graphene structures is a very promising method to improve the separation of CO2 from mixtures with CH4 and N2. The separation properties of the analysed materials are compared with carbon nanotubes having similar diameters or S/V ratio. The presented results have potential importance in the field of CO2 capture and sequestration.

Bilayer graphene formed by passage of current through graphite: evidence for a three-dimensional structure.

The passage of an electric current through graphite or few-layer graphene can result in a striking structural transformation, but there is disagreement about the precise nature of this process. Some workers have interpreted the phenomenon in terms of the sublimation and edge reconstruction of essentially flat graphitic structures. An alternative explanation is that the transformation actually involves a change from a flat to a three-dimensional structure. Here we describe detailed studies of carbon produced by the passage of a current through graphite which provide strong evidence that the transformed carbon is indeed three-dimensional. The evidence comes primarily from images obtained in the scanning transmission electron microscope using the technique of high-angle annular dark-field imaging, and from a detailed analysis of electron energy loss spectra. We discuss the possible mechanism of the transformation, and consider potential applications of 'three-dimensional bilayer graphene'.

Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures.

We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2-CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ~18-20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment).

Applicability of molecular simulations for modelling the adsorption of the greenhouse gas CF4 on carbons.

Tetrafluoromethane, CF(4), is a powerful greenhouse gas, and the possibility of storing it in microporous carbon has been widely studied. In this paper we show, for the first time, that the results of molecular simulations can be very helpful in the study of CF(4) adsorption. Moreover, experimental data fit to the results collected from simulations. We explain the meaning of the empirical parameters of the supercritical Dubinin-Astakhov model proposed by Ozawa and finally the meaning of the parameter k of the empirical relation proposed by Amankwah and Schwarz.

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF6 adsorption data-grand canonical Monte Carlo simulation.

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.

Structures of Pd(CN)2 and Pt(CN)2: intrinsically nanocrystalline materials?

Analysis and modeling of X-ray and neutron Bragg and total diffraction data show that the compounds referred to in the literature as "Pd(CN)(2)" and "Pt(CN)(2)" are nanocrystalline materials containing small sheets of vertex-sharing square-planar M(CN)(4) units, layered in a disordered manner with an intersheet separation of ~3.44 Å at 300 K. The small size of the crystallites means that the sheets' edges form a significant fraction of each material. The Pd(CN)(2) nanocrystallites studied using total neutron diffraction are terminated by water and the Pt(CN)(2) nanocrystallites by ammonia, in place of half of the terminal cyanide groups, thus maintaining charge neutrality. The neutron samples contain sheets of approximate dimensions 30 Å × 30 Å. For sheets of the size we describe, our structural models predict compositions of Pd(CN)(2)·xH(2)O and Pt(CN)(2)·yNH(3) (x ≈ y ≈ 0.29). These values are in good agreement with those obtained from total neutron diffraction and thermal analysis, and are also supported by infrared and Raman spectroscopy measurements. It is also possible to prepare related compounds Pd(CN)(2)·pNH(3) and Pt(CN)(2)·qH(2)O, in which the terminating groups are exchanged. Additional samples showing sheet sizes in the range ~10 Å × 10 Å (y ~ 0.67) to ~80 Å × 80 Å (p = q ~ 0.12), as determined by X-ray diffraction, have been prepared. The related mixed-metal phase, Pd(1/2)Pt(1/2)(CN)(2)·qH(2)O (q ~ 0.50), is also nanocrystalline (sheet size ~15 Å × 15 Å). In all cases, the interiors of the sheets are isostructural with those found in Ni(CN)(2). Removal of the final traces of water or ammonia by heating results in decomposition of the compounds to Pd and Pt metal, or in the case of the mixed-metal cyanide, the alloy, Pd(1/2)Pt(1/2), making it impossible to prepare the simple cyanides, Pd(CN)(2), Pt(CN)(2), or Pd(1/2)Pt(1/2)(CN)(2), by this method.

Molecular dynamics simulation insight into the mechanism of phenol adsorption at low coverages from aqueous solutions on microporous carbons.

MD simulation studies showing the influence of porosity and carbon surface oxidation on phenol adsorption from aqueous solutions on carbons are reported. Based on a realistic model of activated carbon, three carbon structures with gradually changed microporosity were created. Next, a different number of surface oxygen groups was introduced. The pores with diameters around 0.6 nm are optimal for phenol adsorption and after the introduction of surface oxygen functionalities, adsorption of phenol decreases (in accordance with experimental data) for all studied models. This decrease is caused by a pore blocking effect due to the saturation of surface oxygen groups by highly hydrogen-bounded water molecules.

The influence of carbon surface oxygen groups on Dubinin-Astakhov equation parameters calculated from CO2 adsorption isotherm.

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin-Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

A self-repairing, supramolecular polymer system: healability as a consequence of donor-acceptor pi-pi stacking interactions.

A novel supramolecular polymer system, in which the terminal pyrenyl groups of a polyamide intercalate into the chain-folds of a polyimide via electronically-complementary pi-pi stacking, shows both enhanced mechanical properties relative to those of its individual components and facile healing characteristics as a result of the thermoreversibility of non-covalent interactions.

Adsorption from aqueous solutions on opened carbon nanotubes--organic compounds speed up delivery of water from inside.

We report the results of first systematic studies of organic adsorption from aqueous solutions onto relatively long single walled carbon nanotubes (four tubes, in initial and oxidised forms). Using molecular dynamics simulations (GROMACS package) we discuss the behaviour of tube-water as well as tube-adsorbate systems, for three different adsorbates (benzene, phenol and paracetamol).

Open and closed edges of graphene layers.

Edge structures of thermally treated graphite have been studied by means of atomically resolved high-resolution TEM. The method for the determination of a monolayer or more than one layer graphene sheets is established. A series of tilting experiments proves that the zigzag and armchair edges are mostly closed between adjacent graphene layers, and the number of dangling bonds is therefore minimized. Surprisingly bilayer graphene often exhibits AA stacking and is very hard to distinguish from a single graphene layer. Open edge structures with carbon dangling bonds can be found only in a local area where the closed (folding) edge is partially broken.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model.

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO(2), and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Ultrathin graphitic structures and carbon nanotubes in a purified synthetic graphite.

A new class of carbon structure is reported, which consists of microscale graphitic shells bounded by curved and faceted planes containing two to five layers. These structures were originally found in a commercial graphite produced by the Acheson process, followed by a purification treatment. The particles, which could be several hundreds of nanometres in size, were frequently decorated with nanoscale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and that of the nanotubes are intimately connected. The structures are believed to form during a purification process which involves passing an electric current through the graphite in the presence of a reactive gas. In support of this, it is shown that similar particles can be produced in a standard carbon arc apparatus. With their extremely thin graphene walls and high surface areas, the new structures may have a range of useful properties.

Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations.

Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization.

How realistic is the pore size distribution calculated from adsorption isotherms if activated carbon is composed of fullerene-like fragments?

A plausible model for the structure of non-graphitizing carbon is one which consists of curved, fullerene-like fragments grouped together in a random arrangement. Although this model was proposed several years ago, there have been no attempts to calculate the properties of such a structure. Here, we determine the density, pore size distribution and adsorption properties of a model porous carbon constructed from fullerene-like elements. Using the method proposed recently by Bhattacharya and Gubbins (BG), which was tested in this study for ideal and defective carbon slits, the pore size distributions (PSDs) of the initial model and two related carbon models are calculated. The obtained PSD curves show that two structures are micro-mesoporous (with different ratio of micro/mesopores) and the third is strictly microporous. Using the grand canonical Monte Carlo (GCMC) method, adsorption isotherms of Ar (87 K) are simulated for all the structures. Finally PSD curves are calculated using the Horvath-Kawazoe, non-local density functional theory (NLDFT), Nguyen and Do, and Barrett-Joyner-Halenda (BJH) approaches, and compared with those predicted by the BG method. This is the first study in which different methods of calculation of PSDs for carbons from adsorption data can be really verified, since absolute (i.e. true) PSDs are obtained using the BG method. This is also the first study reporting the results of computer simulations of adsorption on fullerene-like carbon models.