Kazutomo Suenaga

Nano-aggregates of single-walled graphitic carbon nano-horns

Abstract We have found a new type of carbon particle produced by the CO 2 laser ablation of carbon at room temperature without a metal catalyst. The product has a powder form of graphitic particles with a uniform size of about 80 nm. An individual particle is composed of an aggregate of many horn-shaped sheaths of single-walled graphene sheets, which we named carbon nano-horns. The nano-horns can be produced at about 10 g/h.

Weaving of organic threads into a crystalline covalent organic framework

Weaving organic threads Woven fabrics are inherently flexible. Liu et al. created a molecular fabric analog using metal-organic frameworks (see the Perspective by Gutierrez-Puebla). Phenanthroline ligands on a copper metal complex directed the addition of organic linkers via imine bonds to create helical organic threads with woven texture. Removing the copper allowed the strands to slide against each other and increased the elasticity of the material 10-fold. Science, this issue p. 365; see also p. 336 A metal-organic framework templates the synthesis of a material made of woven organic polymers. [Also see Perspective by Gutierrez-Puebla] A three-dimensional covalent organic framework (COF-505) constructed from helical organic threads, designed to be mutually weaving at regular intervals, has been synthesized by imine condensation reactions of aldehyde functionalized copper(I)-bisphenanthroline tetrafluoroborate, Cu(PDB)2(BF4), and benzidine (BZ). The copper centers are topologically independent of the weaving within the COF structure and serve as templates for bringing the threads into a woven pattern rather than the more commonly observed parallel arrangement. The copper(I) ions can be reversibly removed and added without loss of the COF structure, for which a tenfold increase in elasticity accompanies its demetalation. The threads in COF-505 have many degrees of freedom for enormous deviations to take place between them, throughout the material, without undoing the weaving of the overall structure.

Mass production of single-wall carbon nanotubes by the arc plasma jet method

Abstract Single-wall carbon nanotubes (SWNTs) were mass-produced by a newly developed DC arc plasma jet method for the evaporation of a metal-doped carbon anode. The production rate of the cottonlike soot was significantly higher than that by conventional DC arc discharge evaporation, and the highest yield was 1.24 g/min. Investigations by scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy indicated that more than 50% of the cottonlike carbon soot was composed of fibrous bundles of SWNTs. Through analysis of the breathing modes in the Raman spectra of the cottonlike soot, the diameter of each SWNT was determined to range from 1.28 to 1.52 nm.

Analysis of the reactivity and selectivity of fullerene dimerization reactions at the atomic level

High-resolution transmission electron microscopy has proved useful for its ability to provide time-resolved images of small molecules and their movements. One of the next challenges in this area is to visualize chemical reactions by monitoring time-dependent changes in the atomic positions of reacting molecules. Such images may provide information that is not available with other experimental methods. Here we report a study on bimolecular reactions of fullerene and metallofullerene molecules inside carbon nanotubes as a function of electron dose. Images of how the fullerenes move during the dimerization process reveal the specific orientations in which two molecules interact, as well as how bond reorganization occurs after their initial contact. Studies on the concentration, specimen temperature, effect of catalyst and accelerating voltage indicate that the reactions can be imaged under a variety of conditions.

Ambipolar field-effect transistor behavior of Gd@C82 metallofullerene peapods

Transport properties of C60 fullerene peapods and Gd@C82 metallofullerene peapods are investigated by using the field effect in a gated structure. The results show that C60 peapods exhibit unipolar p-type characteristics, whereas Gd@C82 peapods show ambipolar both p- and n-type characteristics. This difference in transport behavior can be explained in terms of a bandgap narrowing of the peapods. One of the important findings is that tunable electronic properties of peapods are achieved by using the different types of encapsulated fullerene molecules.

In-Situ Formation of Sandwiched Structures of Nanotube/CuxOy/Cu Composites for Lithium Battery Applications

Development of materials and structures leading to lithium ion batteries with high energy and power density is a major requirement for catering to the power needs of present day electronic industry. Here, we report an in situ formation of a sandwiched structure involving single-walled carbon nanotube film, copper oxide, and copper during the direct synthesis of nanotube macrofilms over copper foils and their electrochemical performance in lithium ion batteries. The sandwiched structure showed a remarkably high reversible capacity of 220 mAh/g at a high cycling current of 18.6 A/g (50 C), leading to a significantly improved electrochemical performance which is extremely high compared to pure carbon nanotube and any other carbon based materials.

Encapsulated and hollow closed-cage structures of WS2 and MoS2 prepared by laser ablation at 450-1050°C

Encapsulated and hollow closed-cage onion-like structures of WS2 and MoS2 were prepared by laser ablation of the corresponding layered structures in argon atmosphere at four varied temperatures. A detailed study for WS2 indicates that only metal-filled onion-like structures are produced at temperatures Tless-than-or-equals, slant650°C, whereas a mixture of metal-filled and hollow structures are produced at Tgreater-or-equal, slanted850°C. The encapsulated metal is identified to be predominantly the metastable β phase of tungsten. Very short tube-like or elongated polyhedral structures are also obtained at high temperatures.

Evidence for active atomic defects in monolayer hexagonal boron nitride: a new mechanism of plasticity in two-dimensional materials.

We report the formation and motion of 4|8 (square-octagon) defects in monolayer hexagonal boron nitride (h-BN). The 4|8 defects, involving less-favorable B-B and N-N bonds, are mobile within the monolayer at high sample temperature (∼ 1000 K) under electron beam irradiation. Gliding of one or two atomic rows along the armchair direction is suggested to be the origin of the defect motion. This represents a completely new mechanism of plasticity in two-dimensional materials.

Syntheses and EELS characterization of water-soluble multi-hydroxyl Gd@C82 fullerenols

Abstract Various water-soluble multi-hydroxyl fullerenes (fullerenols), C60(OH)n, C70(OH)n and C84(OH)n, and a Gd metallo-fullerenols, Gd@C82(OH)n have been synthesized by the Kitazawa method. Elementary chemical analyses indicate that all of these fullerenols have 30–40 hydroxyl groups and 11–15 coordinated water molecules via hydrogen bonds. Electron energy loss spectroscopy (EELS) on Gd@C82 fullerenols shows that the π ∗ peak area in the C K-edge spectra decreases on going from intact Gd@C82 metallofullerene to Gd@C82 fullerenols, indicating an increase in sp3 character of the fullerenols. Furthermore, Gd M4,5-edge EELS spectra show that the encapsulated Gd atom has a trivalent Gd3+ state.

Growth of fullerene-like carbon nitride thin solid films consisting of cross-linked nano-onions

Fullerene-like CNx (x≈0.12) thin solid films were deposited by reactive magnetron sputtering of graphite in a nitrogen and argon discharge on cleaved NaCl and Si(001) substrates at 450 °C. As-deposited films consist of 5 nm diam CNx nano-onions with shell sizes corresponding to Goldberg polyhedra determined by high-resolution transmission electron microscopy. Electron energy loss spectroscopy revealed that N incorporation is higher in the core of the onions than at the perimeter. N incorporation promotes pentagon formation and provides reactive sites for interlinks between shells of the onions. A model is proposed for the formation of CNx nano-onions by continuous surface nucleation and growth of hemispherical shells.