Bromination of Graphene and Graphite

We present a density functional theory study of low density bromination of graphene and graphite, finding significantly different behaviour in these two materials. On graphene we find a new Br2 form where the molecule sits perpendicular to the graphene sheet with an extremely strong molecular dipole. The resultant Br+-Br- has an empty pz-orbital located in the graphene electronic pi-cloud. Bromination opens a small (86meV) band gap and strongly dopes the graphene. In contrast, in graphite we find Br2 is most stable parallel to the carbon layers with a slightly weaker associated charge transfer and no molecular dipole. We identify a minimum stable Br2 concentration in graphite, finding low density bromination to be endothermic. Graphene may be a useful substrate for stabilising normally unstable transient molecular states

Optical Absorption and Raman Spectroscopy Study of the Fluorinated Double-Wall Carbon Nanotubes

Double-wall carbon nanotube (DWNT) samples have been fluorinated at room temperature with varied concentration of a fluorinating agent BrF3. Content of the products estimated from X-ray photoelectron data was equal to CF0.20 and CF0.29 in the case of deficit and excess of BrF3. Raman spectroscopy showed considerable decrease of carbon nanotube amount in the fluorinated samples. Analysis of optical absorption spectra measured for pristine and fluorinated DWNT samples revealed a selectivity of carbon nanotube fluorination. Nanotubes with large chiral angle are more inert to the fluorinating agent used

Electronic Structure of Nitrogen- and Phosphorus-Doped Graphenes Grown by Chemical Vapor Deposition Method

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, respectively. The electronic structure of the films transferred onto SiO2/Si wafers by wet etching of copper substrates is studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy using a synchrotron radiation source. Annealing in an ultra-high vacuum at ca. 773 K allows for the removal of impurities formed on the surface of films during the synthesis and transfer procedure and changes the chemical state of nitrogen in nitrogen-doped graphene. Core level XPS spectra detect a low n-type doping of graphene film when nitrogen or phosphorous atoms are incorporated in the lattice. The electrical sheet resistance increases in the order: graphene < P-graphene < N-graphene. This tendency is related to the density of defects evaluated from the ratio of intensities of Raman peaks, valence band XPS and NEXAFS spectroscopy data. View Full-Tex

Electron spectroscopy of carbon materials: Experiment and theory

We present a comparative spectroscopic study of carbon as graphite, diamond and C60 using C1s K-edge electron energy-loss spectroscopy (EELS), X-ray emission spectroscopy, and theoretical modelling. The first principles calculations of these spectra are obtained in the local density approximation using a self-consistent Gaussian basis pseudo-potential method. Calculated spectra show excellent agreement with experiment and are able to discriminate not only between various carbon hybridisations but also local variation in environment. Core-hole effects on the calculated spectra are also investigated. For the first time, the EEL spectrum of carbyne is calculated

X-ray Spectroscopy Study of Defect Contribution to Lithium Adsorption on Porous Carbon

Lithium adsorption on high-surface-area porous carbon (PC) nanomaterials provides superior electrochemical energy storage performance dominated by capacitive behavior. In this study, we demonstrate the influence of structural defects in the graphene lattice on the bonding character of adsorbed lithium. Thermally evaporated lithium was deposited in vacuum on the surface of as-grown graphene-like PC and PC annealed at 400 °C. Changes in the electronic states of carbon were studied experimentally using surface-sensitive X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NEXAFS data in combination with density functional theory calculations revealed the dative interactions between lithium sp2 hybridized states and carbon π*-type orbitals. Corrugated defective layers of graphene provide lithium with new bonding configurations, shorter distances, and stronger orbital overlapping, resulting in significant charge transfer between carbon and lithium. PC annealing heals defects, and as a result, the amount of lithium on the surface decreases. This conclusion was supported by electrochemical studies of as-grown and annealed PC in lithium-ion batteries. The former nanomaterial showed higher capacity values at all applied current densities. The results demonstrate that the lithium storage in carbon-based electrodes can be improved by introducing defects into the graphene layers

Electron-electron interaction in carbon nanostructures

The electron-electron interaction in carbon nanostructures was studied. A new method which allows to determine the electron-electron interaction constant $\lambda_c$ from the analysis of quantum correction to the magnetic susceptibility and the magnetoresistance was developed. Three types of carbon materials: arc-produced multiwalled carbon nanotubes (arc-MWNTs), CVD-produced catalytic multiwalled carbon nanotubes (c-MWNTs) and pyrolytic carbon were used for investigation. We found that $\lambda_c$=0.2 for arc-MWNTs (before and after bromination treatment); $\lambda_c$ = 0.1 for pyrolytic graphite; $\lambda_c >$ 0 for c-MWNTs. We conclude that the curvature of graphene layers in carbon nanostructures leads to the increase of the electron-electron interaction constant $\lambda_c$.Comment: 12 pages, 18 figures, to be published in the Proceedings of the NATO Advanced Research Workshop on Electron Correlation in New Materials and Nanosystems, NATO Science Series II, Springer, 200