Daisuke Nishio-Hamane

Gold nanoparticles stabilized on nanocrystalline magnesium oxide as an active catalyst for reduction of nitroarenes in aqueous medium at room temperature

Gold nanoparticles deposited on nanocrystalline magnesium oxide is a very efficient catalyst for the reduction of nitroarenes in aqueous medium at room temperature. Sodium borohydride is used as the source of hydrogen for the reduction of nitro groups. This catalytic system selectively reduces the nitro group even in the presence of other sensitive functional groups under very mild conditions in good to excellent yields without the requirement of any promoters. The reaction kinetics of reduction of 4-nitrophenol to 4-aminophenol has been studied by UV-visible spectrophotometry, and its apparent rate constant has been determined and compared with those of other supported gold catalysts. The spent heterogeneous catalyst is recovered by simple centrifugation, and reused for multiple cycles.

An Energy Storage Principle using Bipolar Porous Polymeric Frameworks

Packed with energy: Amorphous covalent triazine-based frameworks were used as a cathode material, with the aim of developing an energy storage principle that can deliver a 2-3 times higher specific energy than current batteries with a high rate capability. The material undergoes a unique Faradaic reaction, as it can be present in both a p-doped and an n-doped state (see picture).

High-pressure and high-temperature phase transitions in FeTiO3 and a new dense FeTi3O7 structure

Abstract High-pressure and high-temperature phase relations of FeTiO3 were investigated up to a pressure of about 74 GPa and 2600 K by synchrotron X-ray diffraction and analytical transmission electron microscopy. We conclude that FeTiO3 ilmenite transforms into the following phase(s) with increasing pressure: FeTiO3 (perovskite) at 20-30 GPa, Fe2TiO4 (Ca2TiO4-type) + TiO2 (OI-type) at 30-44 GPa and high temperature, FeO (wüstite) + TiO2 (OI) at 30-44 GPa and low temperature, and wüstite + FeTi3O7 (orthorhombic phase) above 44 GPa. Among these dense high-pressure polymorphs, FeTi3O7 is a new compound and its structure analysis was tried using particle swarm optimization simulation. This method successfully found a new high-density FeTi3O7 structure, and Rietveld refinement based on this model structure gave an excellent fit with the experimentally obtained X-ray diffraction pattern. This new high-density FeTi3O7 structure consists of polyhedra for monocapped FeO7 prisms, bicapped TiO8 prisms, and tricapped TiO9 prisms, which develop on the b-c plane and stack along the a axis. The dense compound assemblage found in FeTiO3 is promising for investigating the behavior of ABX3 compounds under ultrahigh pressures.

Synthesis of LiNi0.5Mn1.5O4 and 0.5Li2MnO3–0.5LiNi1/3Co1/3Mn1/3O2 hollow nanowires by electrospinning

Hollow wires with thin nanowalls constructed from two-dimensionally connected, highly crystalline nanoparticles were fabricated by electrospinning to create electrode active materials of LiNi0.5Mn1.5O4 (5 V spinel) and 0.5Li2MnO3–0.5LiNi1/3Co1/3Mn1/3O2 (solid-solution type). The resultant materials show large-energy-density properties suitable for use as cathode materials in Li-ion batteries.

Hybrid Amine‐Functionalized Graphene Oxide as a Robust Bifunctional Catalyst for Atmospheric Pressure Fixation of Carbon Dioxide using Cyclic Carbonates

An environmentally-benign carbocatalyst based on amine-functionalized graphene oxide (AP-GO) was synthesized and characterized. This catalyst shows superior activity for the chemical fixation of CO2 into cyclic carbonates at the atmospheric pressure. The developed carbocatalyst exhibits superior activity owing to its large surface area with abundant hydrogen bonding donor (HBD) capability and the presence of well-defined amine functional groups. The presence of various HBD and amine functional groups on the graphene oxide (GO) surface yields a synergistic effect for the activation of starting materials. Additionally, this catalyst shows high catalytic activity to synthesize carbonates at 70 °C and at 1 MPa CO2 pressure. The developed AP-GO could be easily recovered and used repetitively in up to seven recycle runs with unchanged catalyst activity.

Pressure-induced spin transition in FeCO3-siderite studied by X-ray diffraction measurements

We have collected synchrotron X-ray diffraction patterns of FeCO3-siderite after or in-situ laser heating at high pressures to 66 GPa. Diffraction peaks of FeCO3 in all diffraction patterns obtained can be indexed as a trigonal cell. However, calculated cell volumes show an abrupt decrease (about 6.5%) between 47 and 50 GPa at room temperature. This abrupt change of the cell volume on FeCO3 is possibly due to a pressure-induced spin transition of ferrous Fe (HS: high-spin → LS: low-spin). Because cell parameters obtained at high temperature and at pressures above 50 GPa suggest HS state rather than LS state, the Clapeyron slope of the HS-to-LS transition of FeCO3 should be positive.

A new high-pressure polymorph of Ti2O3: implication for high-pressure phase transition in sesquioxides

The post-corundum phase transition has been investigated in Ti2O3 on the basis of synchrotron X-ray diffraction in a diamond anvil cell and transmission electron microscopy. The new polymorph of Ti2O3 was found at about 19 GPa and 1850 K, and this phase was stable even at about 40 GPa. A new polymorph of Ti2O3 can be indexed on a Pnma orthorhombic cell, and the unit-cell parameters are a=7.6965 (19) Å, b=2.8009 (9) Å, c=7.9300 (23) Å, V=170.95 (15) Å3 at 19 GPa, and a=7.8240 (2) Å, b=2.8502 (1) Å, c=8.1209 (3) Å, V=181.10 (1) Å3 at ambient conditions. The Birch–Murnaghan equation of state yields K 0=206 (3) GPa and K′0=4 (fixed) for corundum phase, and K 0=296 (4) GPa and K′0=4 (fixed) for the post-corundum phase. The molar volume decreases by 12% across the phase transition at around 20 GPa. The structural identification was carried out on a recovered sample by the Rietveld method, and a new polymorph of Ti2O3 can be identified as Th2S3-type rather than U2S3-type structure. The transition from corundum-type to Th2S3-type structure accompanies the drastic change of the form of polyhedron: from TiO6 octahedron in the corundum-type to TiO7 polyhedron in the Th2S3-type structures.

Synthesis of Polyester Amide by Carbonylation–Polycondensation Reaction Using Immobilized Palladium Metal Containing Ionic Liquid on SBA-15 as a Phosphine-Free Catalytic System

A novel and simple method for the synthesis of aromatic linear polyester amides has been developed by the carbonylation–polycondensation reaction of aromatic diiodides and aminohydroxy compounds in the presence of ImmPd-IL@SBA-15 catalytic system. Polyester amides with moderate intrinsic viscosity were synthesized in excellent yields using the ImmPd-IL@SBA-15 catalyst and represents efficient heterogeneous and phosphine-free approach for the synthesis of various linear polyester amide derivatives. The ImmPd-IL@SBA-15 catalyst solves the basic problem of catalyst recovery and furnishes good to excellent yield of desired product within short reaction time. The recycled catalyst was characterized using the XPS and TEM analysis. The catalyst was recycled four times without significant loss in activity.Graphical AbstractCatalytic polyester amide synthesis

Structural discrimination of double-walled carbon nanotubes by chiral diporphyrin nanocalipers

In this contribution, we demonstrate the separation of double-walled carbon nanotubes (DWNTs) by host–guest methodology. New chiral diporphyrin nanocalipers with a longer spacer (∼1.9 nm) consisting of carbazole–pyrene–carbazole are rationally designed as a host on the basis of the previous chiral diporphyrin nanocalipers with carbazole–anthracene–carbazole spacer (∼1.4 nm). The chiral nanocalipers are found to recognize the diameter of DWNTs to make diameter distribution much narrower. In addition, the extracted carbon nanotubes (CNTs) exhibited circular dichroism (CD) after removal of the chiral nanocalipers and dissolution in water in the presence of achiral surfactant.

Imayoshiite, Ca3Al(CO3)[B(OH)4](OH)6·12H2O, a new mineral of the ettringite group from Ise City, Mie Prefecture, Japan

Abstract Imayoshiite, Ca3Al(CO3)[B(OH)4](OH)6 ·12H2O, occurs in cavities in the altered gabbro xenolith in the sepentinized dunite exposed at Suisho-dani, Ise City, Mie Prefecture, Japan. Imayoshiite is colourless and transparent with a vitreous lustre and its aggregates are white with a silky lustre. Imayoshiite has a white streak. Its Mohs hardness is 2-3. It is brittle, the cleavage is distinct on {100} and the fracture is uneven. The mineral is uniaxial (-) with the indices of refraction ω = 1.497(2) and ε = 1.470(2) in white light. Imayoshiite is hexagonal, P63, a = 11.0264(11), c = 10.6052(16) Å by powder diffraction and a = 11.04592(2), c = 10.61502(19) Å by single-crystal diffraction. The structural refinement converged to R1 = 2.35%. Imayoshiite is the first member of the ettringite group with both CO3 and B(OH)4 anions.