Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase.

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.

Super flexibility of a 2D Cu-based porous coordination framework on gas adsorption in comparison with a 3D framework of identical composition: framework dimensionality-dependent gas adsorptivities.

Selective synthetic routes to coordination polymers [Cu(bpy)(2)(OTf)(2)](n) (bpy = 4,4'-bipyridine, OTf = trifluoromethanesulfonate) with 2- and 3-dimensionalities of the frameworks were established by properly choosing each different solvent-solution system. They show a quite similar local coordination environment around the Cu(II) centers, but these assemble in a different way leading to the 2D and 3D building-up structures. Although the two kinds of porous coordination polymers (PCPs) both have flexible frameworks, the 2D shows more marked flexibility than the 3D, giving rise to different flexibility-associated gas adsorption behaviors. All adsorption isotherms for N(2), CO(2), and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms, also for CH(4) and water, in addition to these gases. The 3D structure, having hydrophilic and hydrophobic pores, shows the size-selective and quadrupole-surface electrical field interaction dependent adsorption. Remarkably, the 2D structure can accommodate greater amounts of gas molecules than that corresponding to the inherent crystallographic void volume through framework structural changes. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms. The structural diversity of the 2D PCP stems from the breathing phenomenon and expansion/shrinkage modulation.

Dynamic changes in dimensional structures of co-complex crystals.

A two-dimensional flexible porous coordination polymer (2D-PCP) that shows expansion/shrinkage structural transformation accompanied by molecular accommodation was synthesized by control of dimensionality in zero-dimensional and one-dimensional PCPs: The dynamic structural transformation cooperatively proceeds in the solid state with a drastic molecular rearrangement. Kinetics of the structural transformation was investigated.

Preparation and mechanical properties of rubber composites reinforced with carbon nanohorns.

Nitrile butadiene rubber (NBR) composites with single-wall carbon nanohorns (SWNHs, or simply NHs), hole-opened NHs (h-NHs), and carbon black (CB), the most commonly used nanocarbon rubber filler, were prepared, and their mechanical properties were compared. The NBR composites with h-NHs (NBR/h-NH) showed higher tensile strength than those with NHs (NBR/NH), and the tensile strength of NBR/h-NH or NBR/NH was much greater than those of the NBR composites with CB (NBR/CB). At 5 parts per hundred of rubber (phr), the tensile stresses at break of NBR/h-NH was about 1.8 times larger than those of NBR/CB, and the strain at the break, 1.2 times larger. Similarly, at 20 phr, both the tensile strength and strain at the break of NBR/h-NH were 1.4 times larger than those of NBR/CB. NBR/NH showed the highest hardness while having the smallest specific gravity. The present results indicate that NHs and h-NHs have much superior reinforcement effects to CB for NBR rubber matrix.

Enhanced hydrogen adsorptivity of single-wall carbon nanotube bundles by one-step c60-pillaring method.

Single-wall carbon nanotube (SWCNT) bundles were pillared by fullerene (C60) by the cosonication of C60 and SWCNT in toluene to utilize the interstitial pores for hydrogen storage. C60-pillared SWCNTs were confirmed by the shift in the X-ray diffraction peak and the expanded hexagonal and distorted tetragonal bundles revealed by high-resolution transmission electron microscopy. The H2 adsorptivity of the C60-pillared SWCNT bundles was twice that of the original SWCNT bundles, indicating a design route for SWCNT hydrogen storage.

Investigation of the ion storage/transfer behavior in an electrical double-layer capacitor by using ordered microporous carbons as model materials.

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.

Selective optical property modification of double-walled carbon nanotubes by fluorination.

We found that by fluorination of double-walled carbon nanotubes (DWNTs), it is possible to suppress only the Raman radial breathing mode and absorption peaks from the outer (large diameter) tubes of DWNTs. In contrast, Raman signals from the inner shells showed no difference from the pristine DWNTs. The stability of the inner shells of fluorinated DWNTs was also confirmed from the photoluminescence (PL) map and the optical absorption spectra, which only showed the signals from the inner shells of DWNTs, with no distinct change in the optical properties of the inner tubes after fluorination. Our results indicate that once fluorinated, there exists only a weak, if not none, interaction between the inner tube and the outer fluorinated tube, proving that fluorination can be used to suppress the optical properties of carbon nanotubes without interfering the properties of inner tubes. The present finding can be important in electronic and sensor applications, keeping the inner tube from having unwanted contact with other substances that may distract from the inner tube's own characteristics.

Quantum sieving effect of modified activated carbon fibers on H2 and D2 adsorption at 20 K.

Quantum sieving of activated carbon fibers (ACFs) and their fluorides was observed for H(2) and D(2) adsorption at 20 K. Fluorination reduced the slit-shaped pore width of ACFs by 0.2 nm. The activated carbon fibers can act as highly efficient quantum sieves for H(2) and D(2), because the effective size of an H(2) molecule is larger than that of a D(2) molecule due to the uncertainty principle and the molecular size difference between H(2) and D(2) is significant in the micropore space. The D(2)/H(2) selectivity of ACFs evaluated by ideal adsorption solution theory was larger than that of the fluorinated ACFs.