Exfoliated graphite blocks with resilience prepared by room temperature exfoliation and their application for oil-water separation.

Exfoliated graphite (EG) blocks are prepared from the ultra-large flakes of graphite by intercalation of H2SO4 using a large amount of H2O2 at 5 °C and following exfoliation at 30 °C. By the exfoliation in a closed container, EG blocks with the bulk densities of 0.008-0.024 g/cm3 are successfully prepared. The resultant EG blocks have high sorption capacities for a diesel oil, up to 45 g/g. The EG blocks after oil sorption can get certain resilience for compressive stress with high reproducibility by compression-release cycles, which allows us to apply the compression-releasing for the oil sorption-desorption of the EG blocks. The performance of cyclic oil sorption-desorption by compression-releasing of EG block is compared with those of filtration and distillation. Since the resultant EG blocks had sufficient mechanical strength, the continuous removal of oil floating on the water surface is possible, exporting oil through a catheter inserted into the block and connected to a peristaltic pump. By warming up by Joule heating, even a crude oil having high viscosity can be continuously removed from the water with sufficient rate. The high hydrophobicity and lipophilicity of EG make selective removal of oil from water possible.

Constraint spaces in carbon materials.

Nano-sized pores in carbon materials are recently known to give certain constraints to the encapsulated materials by keeping them inside, accompanied with some changes in their structure, morphology, stability, etc. Consequently, nano-sized pores endow the constrained materials with improved performances in comparison with those prepared by conventional processes. These pores may be called "constraint spaces" in carbon materials. Here, we review the experimental results related to these constraint spaces by classifying as nanochannels in carbon nanotubes, nanopores and nanochannels in various porous carbons, and the spaces created by carbon coating.

Buckybowls: Corannulene and Its Derivatives.

Corannulene, a kind of bowl like polycyclic aromatic hydrocarbon (PAH), whose molecule is composed of a central pentagon and five closely adjacent hexagons on the pentagon's five sides, has received great scientific interest among research groups. In this review, the syntheses, characteristic molecule structure and properties of corannulene are clarified, as well as its derivatives with different substituted groups, fused derivatives, metal complex, and derivatives for host guest chemistry. On the basis of reviewing the applications and properties of corannulene together with its derivatives, the potential applications in hydrogen storage and lithium storage were highlighted and prospected.

Carbon nanofibers prepared via electrospinning.

Carbon nanofibers prepared via electrospinning and following carbonization are summarized by focusing on the structure and properties in relation to their applications, after a brief review of electrospinning of some polymers. Carbon precursors, pore structure control, improvement in electrical conductivity,and metal loading into carbon nanofibers via electrospinning are discussed from the viewpoint of structure and texture control of carbon.

Structure and photoactivity of titania derived from nanotubes and nanofibers.

Photoactivity under UV irradiation for the decomposition of methylene blue in water and for the oxidation of NO gas was studied on titania powders derived from titanate nanotube (TNT) and nanofiber (TNF) by annealing at high temperatures, comparing with granular titania (ST-01). Rate constant for methylene blue decomposition k(MB) increased with increasing annealing temperature above 300 degrees C after the conversion from titanate to tinania. It tended to decrease above 700 degrees C, mainly due to the phase transformation from anatase to rutile. The dependences of k(MB) on full width at half maximum intensity (FWHM) were common for three samples, a sharp maximum at around 0.4 degrees in FWHM, but TNF-derived sample gave much higher maximum than ST-01. Change in fraction of oxidized NO with annealing temperature showed a plateau at around 50% and then decreased abruptly by high temperature annealing. Starting from TNT and TNF has an advantage to form fine particles by annealing above 300 degrees C, giving high photoactivity due to high crystallinity and high adsorptivity particularly for methylene blue.

Application of carbon-coated TiO2 for decomposition of methylene blue in a photocatalytic membrane reactor.

An application of carbon-coated TiO(2) for decomposition of methylene blue (MB) in a photocatalytic membrane reactor (PMR), coupling photocatalysis and direct contact membrane distillation (DCMD) was investigated. Moreover, photodegradation of a model pollutant in a batch reactor without membrane distillation (MD) was also examined. Carbon-modified TiO(2) catalysts containing different amount of carbon and commercially available TiO(2) (ST-01) were used in this study. The carbon-coated catalyst prepared from a mixture of ST-01 and polyvinyl alcohol in the mass ratio of 70/30 was the most effective in degradation of MB from all of the photocatalysts applied. Photodecomposition of MB on the recovered photocatalysts was lower than on the fresh ones. The photodegradation of MB in the PMR was slower than in the batch reactor, what probably resulted from shorter time of exposure of the catalyst particles to UV irradiation. The MD process could be successfully applied for separation of photocatalyst and by-products from the feed solution.

Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process.

Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.

Dependence of photocatalytic activity of anatase powders on their crystallinity.

Structural changes in anatase phase in four TiO(2) photocatalysts with annealing at high temperatures were followed by evaluating crystallite size and lattice strain of anatase phase separately and measuring the content of anatase. The rate constant k for the decomposition of methylene blue in its aqueous solution under UV irradiation was determined as a measure of photocatalytic activity. Marked dependences in crystallinity improvement, i.e., the growth of crystallite and the decrease in lattice strain, and in phase transformation from anatase to rutile phases of TiO(2) on annealing temperature was observed above 500 degrees C, depending on starting photocatalysts used. The phase transformation to rutile started after reaching of crystallite size to about 32 nm and of lattice strain to about 0.5 x 10(-3). Rate constant k was found to depend on both crystallite size and lattice strain of anatase; it increased with increasing crystallite size up to about 32 nm and decreasing lattice strain down to about 0.5 x 10(-3). Further increase in crystallite size and decrease in lattice strain induced the decrease in rate constant k, mainly due to the partial transformation of anatase to rutile. The present results showed that the activity of the photocatalysts was possible to be improved by annealing at a high temperature, by selecting an optimal condition of annealing for getting a high crystallinity in anatase phase and no phase transformation to rutile phase.

Comparative study of carbon dioxide and nitrogen atmospheric effects on the chemical structure changes during pyrolysis of phenol-formaldehyde spheres.

The effect of CO(2) atmosphere on the chemical structure changes of resol-type phenol-formaldehyde spheres during pyrolysis was investigated, in comparison with that of N(2) atmosphere, using FT-IR, TGA, and elemental analysis techniques. It was found that, in contrast to the expectation that CO(2) may act as an oxidizing agent at high temperature, it behaves very similar to N(2) during pyrolysis of PF spheres up to 700 degree C, but results in a somewhat different extent of some specific reactions. That is, although the reactions occurring up to 700 degree C were dominated by crosslinking and/or polyaromatization under both CO(2) and N(2) atmospheres, fewer alkyl-phenolic ether bonds were formed under CO(2) than under N(2). As a consequence, the samples carbonized under CO(2) at 700 degree C were found to have more pendant groups on the edge carbon atoms of carbon in the carbonized samples than those prepared under N(2) atmosphere.

Sorption kinetics of heavy oil into porous carbons.

Sorption kinetics of heavy oil into porous carbons was evaluated by a concept of liquid sorption coefficient obtained from the weight increase of heavy oil with sorption time, which was measured by a wicking test. Exfoliated graphite, carbonized fir fibers and carbon fiber felts were used as porous materials. It was found that the liquid sorption coefficient of fibrous carbons was twice larger than that of exfoliated graphite. Such a difference in the liquid sorption coefficient between the exfoliated graphite and two fibrous carbons was caused by a difference in effective sorption porosity and tortuosity between them. For the exfoliated graphite and carbonized fir fibers, the liquid sorption coefficient and the effective sorption porosity were strongly dependent on their density. The maximum values of both liquid sorption coefficient and effective sorption porosity of the exfoliated graphite were shown at the bulk density around 16 kg/m3. The liquid sorption coefficient of the carbonized fir fibers increased with increasing the density in the range from 6 to 30 kg/m3. When the carbonized fir fibers were densified above 30 kg/m3, the sorption rate was saturated. On the other hand, the sorption kinetics into the carbon fiber felt was almost independent of the bulk density, because the density of the carbon fiber felt is not effective for the pore structure. The effect of bulk density on the sorption kinetics could be supported from an analysis of pore structure of the porous carbons with different densities, which was measured by mercury porosimeter.