Fluorination as effective method for tuning the electromagnetic response of graphene

Fluorinated graphene (FG) has been obtained by a fluorination of thermally exfoliated graphite fluoride C2F layers using a gaseous mixture of BrF3 and Br2 at room temperature. Comparative study of electromagnetic (EM) response of thin FG films after recovering their conductivity via different methods is presented in microwave (GHz) and terahertz (THz) frequency ranges. We discovered that fluorination can be used as promising tool for producing tunable EM interference (EMI) shielding materials, combining reflective and absorptive layers

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

Controlling pyridinic, pyrrolic, graphitic, and molecular nitrogen in multi-wall carbon nanotubes using precursors with different N/C ratios in aerosol assisted chemical vapor deposition

Nitrogen-containing multi-wall carbon nanotubes (N-MWCNTs) were synthesized using aerosol assisted chemical vapor deposition (CVD) techniques in conjunction with benzylamine:ferrocene or acetonitrile: ferrocene mixtures. Different amounts of toluene were added to these mixtures in order to change the N/C ratio of the feedstock. X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy detected pyridinic, pyrrolic, graphitic, and molecular nitrogen forms in the N-MWCNT samples. Analysis of the spectral data indicated that whilst the nature of the nitrogen-containing precursor has little effect on the concentrations of the different forms of nitrogen in N-MWCNTs, the N/C ratio in the feedstock appeared to be the determining factor. When the N/C ratio was lower than ca. 0.01, all four forms existed in equal concentrations, for N/C ratios above 0.01, graphitic and molecular nitrogen were dominant. Furthermore, higher concentrations of pyridinic nitrogen in the outer shells and N2 molecules in the core of the as-produced N-MWCNTs suggest that the precursors were decomposed into individual atoms, which interacted with the catalyst surface to form CN and NH species or in fact diffused through the bulk of the catalyst particles. These findings are important for a better understanding of possible growth mechanisms for heteroatom-containing carbon nanotubes (CNTs) and therefore paving the way for controlling the spatial distribution of foreign elements in the CNTs using CVD processes

Step-Wise Computational Synthesis of Fullerene C60 derivatives. 1.Fluorinated Fullerenes C60F2k

The reactions of fullerene C60 with atomic fluorine have been studied by unrestricted broken spin-symmetry Hartree-Fock (UBS HF) approach implemented in semiempirical codes based on AM1 technique. The calculations were focused on a sequential addition of fluorine atom to the fullerene cage following indication of the cage atom highest chemical susceptibility that is calculated at each step. The effectively-non-paired-electron concept of the fullerene atoms chemical susceptibility lays the foundation of the suggested computational synthesis. The obtained results are analyzed from energetic, symmetry, and the composition abundance viewpoints. A good fitting of the data to experimental findings proves a creative role of the suggested synthesis methodology.Comment: 33 pages, 11 figures, 2 tables, 2 chart

Edge state magnetism in zigzag-interfaced graphene via spin susceptibility measurements

Development of graphene spintronic devices relies on transforming it into a material with a spin order. Attempts to make graphene magnetic by introducing zigzag edge states have failed due to energetically unstable structure of torn zigzag edges. Here, we report on the formation of nanoridges, i.e., stable crystallographically oriented fluorine monoatomic chains, and provide experimental evidence for strongly coupled magnetic states at the graphene-fluorographene interfaces. From the first principle calculations, the spins at the localized edge states are ferromagnetically ordered within each of the zigzag interface whereas the spin interaction across a nanoridge is antiferromagnetic. Magnetic susceptibility data agree with this physical picture and exhibit behaviour typical of quantum spin-ladder system with ferromagnetic legs and antiferromagnetic rungs. The exchange coupling constant along the rungs is measured to be 450 K. The coupling is strong enough to consider graphene with fluorine nanoridges as a candidate for a room temperature spintronics material

Bromination of double-walled carbon nanotubes

Double-walled carbon nanotubes (DWCNTs) synthesized by catalytic chemical vapor deposition (CCVD) have been functionalized by bromine vapor at room temperature. At least two different bromine species were detected in the product using X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis. The primary form is negatively charged Br2 molecules exhibiting an intense resonance at ∼238 cm−1 in the Raman spectrum. The electron transfer from the nanotubes to the adsorbed molecules is detected from C 1s XPS and near-edge X-ray absorption fine structure spectra. The optical absorption spectra reveal that although the metallic nanotubes are more reactive to Br2, the outer semiconducting nanotubes also readily interact with Br2 adsorbates. The secondary bromine form is attributed to covalent C-Br bonding, and its possible sources are discussed in the light of quantum-chemical calculations. Analysis of the XPS, Raman, and optical absorption spectra of the Br-DWCNTs annealed at 100-170 ° C indicates preservation of a part of bromine molecules in samples that affects the electronic and vibration properties of nanotubes

Thermal Decomposition of Co-Doped Calcium Tartrate and Use of the Products for Catalytic Chemical Vapor Deposition Synthesis of Carbon Nanotubes.

Thermal decomposition of Co-doped calcium tartrate in an inert atmosphere or air was studied using thermogravimetric analysis and X-ray absorption fine structure (XAFS) spectroscopy. It was shown that the powder substance containing 4 at.% of cobalt completely decomposes within 650-730 °C, depending on the environment, and the formation of Co clusters does not proceed before 470 °C. The products of decomposition were characterized by transmission electron microscopy, XAFS, and X-ray photoelectron spectroscopy. Surfaceoxidized Co metal nanoparticles as large as ∼5.6 ( 1.2 nm were found to form in an inert atmosphere, while the annealing in air led to a wide distribution of diameters of the nanoparticles, with the largest nanoparticles (30-50 nm) mainly present as a Co3O4 phase. It was found that the former nanoparticles catalyze the growth of CNTs from alcohol while a reducing atmosphere is required for activation of the latter nanoparticles. We propose the scheme of formation of CaO-supported catalyst from Co-doped tartrate, depending on the thermal decomposition conditions