Stability and dynamics of vacancy in graphene flakes: Edge effects

a b s t r a c t Density functional theory calculations show that graphene flakes with monovacancy at the edge are energetically more stable than the flakes with vacancy in the middle. The energies of metastable and transition states for one step of vacancy motion towards the edge are calculated. We show that thermally activated motion of vacancy towards the edge occurs even at room temperature whereas the probability of return motion back to the middle is negligible. Molecular dynamics simulations of the vacancy motion in graphene flakes confirm this conclusion. The obtained results explain the mechanisms driving structural transformations in graphene

Electrostatic force between a charged sphere and a planar surface: A general solution for dielectric materials

Using the bispherical coordinate system, an analytical solution describing the electrostatic force between a charged dielectric sphere and a planar dielectric surface is presented. This new solution exhibits excellent numerical convergence, and is sufficiently general as to allow for the presence of charge on both the sphere and the surface. The solution has been applied to two examples of sphere-plane interactions chosen from the literature, namely, (i) a charged lactose sphere interacting with a neutral glass surface and (ii) a charged polystyrene sphere interacting with a neutral graphite surface. Theory suggests that in both cases the electrostatic force makes a major contribution to the experimentally observed attraction at short sphere-plane separations, and that the force is much longer ranged than previously suggested. © 2014 AIP Publishing LLC

A novel bismuth-based metal-organic framework for high volumetric methane and carbon dioxide adsorption

Solvothermal reaction of H4L (L = biphenyl-3,3’,5,5’-tetracarboxylate) and Bi(NO3)3·(H2O)5 in a mixture of DMF/MeCN/H2O in the presence of piperazine and nitric acid at 100 oC for 10 h affords the solvated metal-organic polymer [Bi2(L)1.5(H2O)2]·(DMF)3.5·(H2O)3 (NOTT-220-solv). A single crystal X-ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non-interpenetrated structure comprising binuclear {Bi2} centres bridged by tetracarboxylate ligands. NOTT-220-solv shows a 3,6-connected network having a new framework topology with a {4·62}2{42·65·88}{62·8} point symbol. The desolvated material NOTT-220a shows exceptionally high adsorption uptakes for CH4 and CO2 on a volumetric basis at moderate pressures and temperatures with a CO2 uptake of 553 gL-1 (20 bar, 293 K) with a saturation uptake of 688 gL-1 (1 bar, 195 K). The corresponding CH4 uptake of 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) is within the top three MOF materials under the same conditions, surpassed only by PCN-14 and Ni-MOF-74 (230 and 190 V(STP)/V 35 Bar, 298 K). The maximum CH4 uptake for NOTT-220a was recorded at 20 bar and 195 K to be 287 V(STP)/V, while H2 uptake of NOTT-220a at 20 bar, 77 K is 42 gL-1. These gas uptakes have been modelled by Grand Canonical Monte Carlo (GCMC) and Density Functional Theory (DFT) calculations, which confirm the experimental data and give insights into the nature of the binding sites of CH4 and CO2 in this porous hybrid material

The effect of like-charge attraction on aerosol growth in the atmosphere of Titan

The formation of aerosols in the atmosphere of Titan is based extensively onion-neutral chemistry and physical condensation processes. Herein it is shown that the formation of aerosols may also occur through an alternative pathway that involves the physical aggregation of negatively charged particles, which are known to be abundant in the satellite's atmosphere. It is shown that, given the right circumstances, like-charged particles with a dielectric constant characteristic of nitrated hydrocarbons have sufficient kinetic energy to overcome any repulsive electrostatic barrier that separates them and can subsequently experience an attractive interaction at very short separation. Aerosol growth can then unfold through a charge scavenging process, whereby nitrated aggregates preferentially grow by assimilating smaller like-charged particles. Since hydrocarbon aerosols have much lower dielectric constants, it is shown that a similar mechanism involving hydrocarbon particles will not be as efficient. As a consequence of this proposed growth mechanism, it is suggested that the lower atmosphere of Titan will be enriched in nitrogen-containing aerosols

Adsorbate-induced curvature and stiffening of graphene

The adsorption of the alkane tetratetracontane (TTC, C44H90) on graphene induces the formation of a curved surface stabilized by a gain in adsorption energy. This effect arises from a curvature-dependent variation of a moiré pattern due to the mismatch of the carbon−carbon separation in the adsorbed molecule and the period of graphene. The effect is observed when graphene is transferred onto a deformable substrate, which in our case is the interface between water layers adsorbed on mica and an organic solvent, but is not observed on more rigid substrates such as boron nitride. Our results show that molecular adsorption can be influenced by substrate curvature, provide an example of two-dimensional molecular self-assembly on a soft, responsive interface, and demonstrate that the mechanical properties of graphene may be modified by molecular adsorption, which is of relevance to nanomechanical systems, electronics, and membrane technology

Methane adsorption in metal-organic frameworks containing nanographene linkers: a computational study

Metal-organic framework (MOF) materials are known to be amenable to expansion through elongation of the parent organic linker. For a family of model (3,24)-connected MOFs with the rht topology, in which the central part of organic linker comprises a hexabenzocoronene unit, the effect of the linker type and length on their structural and gas adsorption properties is studied computationally. The obtained results compare favourably with known MOF materials of similar structure and topology. We find that the presence of a flat nanographene-like central core increases the geometric surface area of the frameworks, sustains additional benzene rings, promotes linker elongation and the efficient occupation of the void space by guest molecules. This provides a viable linker modification method with potential for enhancement of uptake for methane and other gas molecules

A robust binary supramolecular organic framework (SOF) with high CO2 adsorption and selectivity

A robust binary hydrogen-bonded supramolecular organic framework (SOF-7) has been synthesized by solvothermal reaction of 1,4-bis-(4-(3,5-dicyano-2,6 dipyridyl)dihydropyridyl)benzene (1) and 5,5’-bis-(azanediyl)-oxalyl-diisophthalic acid (2). Single crystal X-ray diffraction analysis shows that SOF-7 comprises 2 and 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene (3), the latter formed in situ from the oxidative dehydrogenation of 1. SOF-7 shows a three-dimensional four-fold interpenetrat-ed structure with complementary O−H···N hydrogen bonds to form channels that are decorated with cyano- and amide-groups. SOF-7 exhibits excellent thermal stability and sol-vent and moisture durability, as well as permanent porosity. The activated desolvated material SOF-7a shows high CO2 sorption capacity and selectivity compared with other po-rous organic materials assembled solely through hydrogen bonding

C 2008 Theoretical study of the structures and electronic properties of all-surface KI and CsI nanocrystals encapsulated in single walled carbon nanotubes

The structural and electronic properties of all-surface KI and CsI crystals encapsulated in single-walled carbon nanotubes are investigated theoretically with an ionic and atomistic approach using the GULP program. The short-range interactions, derived from Dirac-Fock wavefunctions, were augmented with damped dipole-dipole and dipole-quadrupole dispersive attractions. The uncorrelated interionic interactions computed using the relativistic crystal ion and relativistic integral programs accounted for anion in-crystal modifications while being exact given the ion wavefunctions. All the short-range correlation energies and the uncorrelated interactions between the ions and carbon atoms were computed using the density functional theory of a uniform electron gas of infinite extent. Unphysical self-interactions were removed by scaling the exchange interaction with a Rae factor derived from a study of the adsorption of noble gases on graphite. The predictions for the nonencapsulated crystals agreed well with those previously derived from a global analytic theory based on the Born model. This provided a good description of the contraction of the interplane distance ͑b͒ relative to the separation ͑R e ͒ in the rocksalt structured bulk material although failing to account for the observed dilation of the intraplane ionic separations ͑a͒. Introduction of the interactions with the nanotube wall, including the ion-nanotube dispersive attractions, increased the predicted a values although these were still significantly smaller than experiment. The predicted b separations were reduced compared with those for the nonencapsulated crystals to values significantly less than observed. It is explained why introducing any ion-nanotube interactions that are sufficiently attractive as to reproduce the experimental a values must significantly underestimate the b separations. The partial transfer of anion electrons to the nanotube carbon atoms, not considered hitherto, was described by decomposing the intra-atomic interactions of both the nanotube -and the iodide 5p-electrons into an effective one-electron term plus the repulsion between electrons in the same orbital. These energies were derived from electronic structure computations with the additional interspecies electrostatic repulsions derived from the GULP program. Structural predictions are presented as a function of the number ͑n͒ of electrons transferred from each anion. For both KI and CsI, the structure predicted by that computation, which minimized the total energy, in contrast to the other calculations, agreed well with experiment reproducing both the significant dilation of a and the smaller contraction of b. The respective n values ͑n t ͒ predicting the lowest energies are 0.278 and 0.285. These results are supported by comparing the experimental frequencies of Raman modes attributable to vibrations of nanotubes encapsulating KI with the corresponding frequencies for systems where independently known numbers of electrons were transferred to the nanotubes. In both the encapsulated KI and CsI systems, the charge transfer is driven by the reduction of the electron repulsion on delocalizing some anion charge over the significantly greater number of nanotube carbon atoms. A simplified analytic model, which reproduces the charge transfers, explains why n t is slighter larger for CsI and also predicts that n t will be insensitive to the structure of the nanotube