We report the synthesis and evidence of graphene fluoride, a two-dimensional wide bandgap semiconductor derived from graphene. Graphene fluoride exhibits hexagonal crystalline order and strongly insulating behavior with resistance exceeding 10 GΩ at room temperature. Electron transport in graphene fluoride is well described by variable-range hopping in two dimensions due to the presence of localized states in the band gap. Graphene obtained through the reduction of graphene fluoride is highly conductive, exhibiting a resistivity of less than 100 kΩ at room temperature. Our approach provides a new path to reversibly engineer the band structure and conductivity of graphene for electronic and optical applications.
An ordered microporous carbon, which was prepared with zeolite as a template, was used as a model material to understand the ion storage/transfer behavior in electrical double-layer capacitor (EDLC). Several types of such zeolite-templated carbons (ZTCs) with different structures (framework regularity, particle size and pore diameter) were prepared and their EDLC performances were evaluated in an organic electrolyte solution (1 M Et(4)NBF(4)/propylene carbonate). Moreover, a simple method to evaluate a degree of wettability of microporous carbon with propylene carbonate was developed. It was found that the capacitance was almost proportional to the surface area and this linearity was retained even for the carbons with very high surface areas (>2000 m(2) g(-1)). It has often been pointed out that thin pore walls limit capacitance and this usually gives rise to the deviation from linearity, but such a limitation was not observed in ZTCs, despite their very thin pore walls (a single graphene, ca. 0.34 nm). The present study clearly indicates that three-dimensionally connected and regularly arranged micropores were very effective at reducing ion-transfer resistance. Despite relatively small pore diameter ZTCs (ca. 1.2 nm), their power density remained almost unchanged even though the particle size was increased up to several microns. However, when the pore diameter became smaller than 1.2 nm, the power density was decreased due to the difficulty of smooth ion-transfer in such small micropores.
The chemical bonding and the electronic structures of C 60 F x and C 70 F x were investigated by near edge X-ray absorption fine structure (NEXAFS) spectroscopy and UV photoemission spectroscopy (UPS), which are useful methods for examining the unoccupied and the occupied states, respectively. With these results and XPS measurements, we derived the electronic energy diagram of C 60 F x and discussed the change of the electronic structure from that of C 60 by fluorination. The energies of the LUMO and the Fermi level of solid C 60 F 48 were estimated to be -5.0 and -5.4 eV below the vacuum level, indicating that highly doped C 60 F x is a strong electron acceptor. The electronic absorption spectra of C 60 F x solutions deep into the vacuumultraviolet region were also measured, and the isomerism of C 60 F x was discussed by comparing the observed results with theoretical simulations.
An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.
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