Shoichi Toh

Hydrogen storage in Pd nanocrystals covered with a metal–organic framework

Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

Fabrication and characterization of anatase/rutile–TiO2 thin films by magnetron sputtering: a review

Abstract Ceramic-based nanocomposites were reviewed, emphasizing the newly developed concept of material design for ceramics. First, characteristics of the nanocomposites observed by previous researchers were summarized as, significant or moderate improvement in strength, drastic change of the fracture mode from intergranular fracture of monolithic ceramics to transgranular fracture of nanocomposites, moderate enhancement of fracture toughness, improvement of other mechanical properties, and observations of dislocations. Second, several mechanisms proposed previously to explain these characteristics were reviewed. Third, our strengthening and toughening mechanisms of nanocomposites on the basis of dislocation activities were explained. In nanocomposites, the highly localized residual stresses in the matrix grains are generated by the mismatch of thermal expansion coefficients between the matrix and the dispersed particles, and the dislocations are yielded during the cooling process after sintering. These dislocations then release the tensile residual stresses intrinsically existing in the matrix grains of sintered ceramics and improve the strength of the materials. In addition, as these dislocations cannot move at room temperature the sessile dislocations in the matrix operate as nano-crack nuclei in a frontal process zone (FPZ) ahead of the crack tip when the tip of a propagating crack approaches this area. Therefore, the size of the FPZ is expanded and as a result the fracture toughness is improved. Finally, estimation of the critical FPZ size was explained in order to clarify its toughening mechanism in nanocomposites.

Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing Ability

Pd(x)Ru(1-x) solid solution alloy nanoparticles were successfully synthesized over the whole composition range through a chemical reduction method, although Ru and Pd are immiscible at the atomic level in the bulk state. From the XRD measurement, it was found that the dominant structure of Pd(x)Ru(1-x) changes from fcc to hcp with increasing Ru content. The structures of Pd(x)Ru(1-x) nanoparticles in the Pd composition range of 30-70% consisted of both solid solution fcc and hcp structures, and both phases coexist in a single particle. In addition, the reaction of hydrogen with the Pd(x)Ru(1-x) nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepared Pd(x)Ru(1-x) nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.

Nanosize-Induced Drastic Drop in Equilibrium Hydrogen Pressure for Hydride Formation and Structural Stabilization in Pd–Rh Solid-Solution Alloys

We have synthesized and characterized homogeneous solid-solution alloy nanoparticles of Pd and Rh, which are immiscible with each other in the equilibrium bulk state at around room temperature. The Pd-Rh alloy nanoparticles can absorb hydrogen at ambient pressure and the hydrogen pressure of Pd-Rh alloys for hydrogen storage is dramatically decreased by more than 4 orders of magnitude from the corresponding pressure in the metastable bulk state. The solid-solution state is still maintained in the nanoparticles even after hydrogen absorption/desorption, in contrast to the metastable bulks which are separated into Pd and Rh during the process.

High-pressure torsion of pure cobalt: hcp-fcc phase transformations and twinning during severe plastic deformation

Cobalt with low stacking fault energy in the forms of bulk and powders was severely deformed using high-pressure torsion to investigate the influence of grain size on allotropic phase transformations. A phase transformation occurred from metastable fcc to hcp until the average grain size reached the submicrometer level. However, an hcp → fcc phase transformation with nanotwin formation occurred together with the formation of a distorted hcp structure when the grain size was reduced well to the nanometer level (∼20 nm). Mechanical and magnetic properties were also investigated.

Corn-shape carbon nanofibers with dense graphite synthesized by microwave plasma-enhanced chemical vapor deposition

Corn-shape carbon nanofibers (CCNFs) with metal-free tips have been synthesized by a microwave plasma-enhanced chemical-vapor deposition method using CH4 and H2 gasses. The CCNFs were grown on Ni/SiO2/Si and Ni/Mo mesh substrates using a bias-enhanced growth method, and they were analyzed by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The cones are composed of cylindrical pure graphite sheets, and have nanometer-sized tips and roots. The tips’ apex angles of CCNFs have cone angles of 20°, 39°, and 60° depending on the growth conditions such as substrate temperature.

Enhanced magnetization in highly crystalline and atomically mixed bcc Fe–Co nanoalloys prepared by hydrogen reduction of oxide composites

Fe(x)Co(100-x) nanoalloys (NAs) with 20 ≤ x ≤ 80 were prepared by hydrogen reduction of Fe-Co oxide nano-composites, which were composed of mixed phases (or domains) of Fe(2)O(3) and CoO. In situ X-ray diffraction (XRD) measurements using synchrotron radiation clearly showed development of a solid-solution Fe-Co phase by hydrogen reduction from the oxide composites. High-resolution transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM and powder XRD revealed that Fe-Co NAs form a single crystal structure and the two elements are mixed homogeneously. The saturation magnetization depends on the size and metal composition and shows the highest value (250 emu g(-1)) for the Fe(70)Co(30) NA in the size range of 30-55 nm, which is comparable to that of the Fe(70)Co(30) bulk alloy (245 emu g(-1)). This high magnetization is attributable to high crystallinity and homogeneous mixing of constituent atoms, which are attained by thermal treatment of oxide phases under a hydrogen atmosphere.

Transmission electron microscopy characterization of nanorods in BaNb2O6-doped ErBa2Cu3O7−δ films

BaNb2O6-doped microstructures as artificial pinning centers in ErBa2Cu3O7−δ films were studied by transmission electron microscopy. The presence of nanorods, which contain niobium, was confirmed from bright-field images and elemental map images. The crystal structure of the nanorod was determined to be cubic perovskite. The lattice constant of nanorods in the ErBa2Cu3O7−δ film was in good agreement with the lattice constant of Ba(Er0.5Nb0.5)O3. Furthermore, parallel Moire fringes were observed in the bright-field images. It has never been confirmed by any other researchers that BaNb2O6 doped into the ErBa2Cu3O7−δ film transforms to Ba(Er0.5Nb0.5)O3 nanorods with a perovskite structure.BaNb2O6-doped microstructures as artificial pinning centers in ErBa2Cu3O7−δ films were studied by transmission electron microscopy. The presence of nanorods, which contain niobium, was confirmed from bright-field images and elemental map images. The crystal structure of the nanorod was determined to be cubic perovskite. The lattice constant of nanorods in the ErBa2Cu3O7−δ film was in good agreement with the lattice constant of Ba(Er0.5Nb0.5)O3. Furthermore, parallel Moire fringes were observed in the bright-field images. It has never been confirmed by any other researchers that BaNb2O6 doped into the ErBa2Cu3O7−δ film transforms to Ba(Er0.5Nb0.5)O3 nanorods with a perovskite structure.

Transformation of graphite to lonsdaleite and diamond in the Goalpara ureilite directly observed by TEM

Abstract This study reports on the structural relationship between graphite, lonsdaleite, and diamond extracted from the Goalpara ureilite and propose a model for the formation of lonsdaleite and diamond in these stony meteorites. The study is based on data from reflected-light microscopy and laser Raman spectroscopy of a polished thin section (PTS) of the Goalpara ureilite and X-ray powder diffraction (XRPD) analyses of the grains taken out of it. Selected-area electron diffraction (SAED) analyses and high-resolution TEM (HRTEM) observations were carried out in the three unique directions of pristine graphite with two thin slices prepared from a carbon grain directly taken out of a PTS. SAED patterns reveal the relative crystal-axes orientations between graphite (Gr), lonsdaleite (Lo), and diamond (Di) as (001)Gr//(100)Lo//(111)Di, [210]Gr//[001]Lo//[21̅1̅]Di, and (12̅0)Gr//(1̅20)Lo//(02̅2)Di. The shapes of diffraction spots in the SAED patterns reveal that the transformation of graphite to lonsdaleite and diamond is initiated by sliding of hexagonal carbon planes of graphite along the [210] of the graphite structure. These results suggest that lonsdaleite and diamond in ureilites formed directly from graphite through boat-type buckling and chair-type puckering of hexagonal carbon planes of graphite, respectively. The results of this study confirm the shock origin of diamond in ureilites.

Synthesis, microstructure and photoluminescence of well-aligned ZnO nanorods on Si substrate

Abstract Well-aligned zinc oxide (ZnO) nanorods were densely grown on Si substrate using ZnO thin-film seed layer without any catalysts and/ or additives by a simple solid–vapour phase thermal sublimation technique. The growth mechanism can be interpreted as self-catalyst of zinc particles based on vapour–solid (VS) mechanism. High-resolution transmission electron microscopy (HRTEM) image and selected area electron diffraction (SAED) pattern confirmed that the single-crystalline growth of the nanorods were preferentially along c-axis of hexagonal crystal system. High-crystal quality ZnO nanorods with strong near band edge emission centred at 380 nm can be achieved on Si substrate by the introduction of sufficient oxygen during the nanorod growth processing.