Yoshitaka Matsushita

General Synthesis and Structural Evolution of a Layered Family of Ln8(OH)20Cl4·nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y)

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water molecules per formula weight, n, changed from 6.6 for the high-hydration Gd sample to 6.0 for the low-hydration Gd sample. Also, the hydration number usually decreased with increasing atomic number; e.g., n = 7.4, 6.3, 7.2, and 6.6 for high-hydration Nd, Sm, Eu, and Gd, and n = 6.0, 5.8, 5.6, 5.4, and 4.9 for low-hydration Gd, Tb, Dy, Ho, and Er. The variation in the average Ln-O bond length with decreasing size of the lanthanide ions is also discussed. This family of layered lanthanide compounds highlights a novel chemistry of interplay between crystal structure stability and coordination geometry with water molecules.

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity

In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

New Layered Rare‐Earth Hydroxides with Anion‐Exchange Properties

We report the synthesis of a new series of layered hydroxides based on rare-earth elements with a composition of RE(OH)2.5Cl(0.5).0.8 H2O (RE: Eu, Tb, etc.) through the homogeneous precipitation of RECl3.x H2O with hexamethylenetetramine (HMT). Rietveld analysis combined with direct methods revealed an orthorhombic layered structure comprising a positively charged layer of [RE(OH)2.5-(H2O)0.8]0.5+ and interlayer Cl- ions. The Cl- ions were readily exchangeable for various anions (NO3-, SO4(2-), dodecylsulfonate, etc.) at ambient temperature. Photoluminescence studies showed that the compounds display typical RE3+ emission. With rare-earth-based host layers and tunable interlayer guests, the new compounds may be of interest for optoelectronic, magnetic, catalytic, and biomedical materials.

Structural Disorder and Diffusional Pathway of Oxide Ions in a Doped Pr2NiO4-Based Mixed Conductor

MEM nuclear density analysis from neutron diffraction data measured in situ at 1015.6 degrees C has indicated the two-dimensional network of curved O2-O3-O2 oxide-ion diffusion paths on the (Pr,La)-O layer in a K2NiF4-type structured oxide-ionic and electronic mixed conductor (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+delta.

New Pyrochlore Oxide Superconductor RbOs2O6

We report the discovery of a new pyrochlore oxide superconductor RbOs 2 O 6 . The compound crystallizes in the same β-pyrochlore structure as the recently discovered superconductor KOs 2 O 6 , where Os atoms form a corner-sharing tetrahedral network called the pyrochlore lattice with Rb or K atoms in the cage. Resistivity, magnetic susceptibility and specific heat measurements on polycrystalline samples evidence a bulk superconductivity with T c =6.3 K.

Superconductivity and Structural Phase Transitions in Caged Compounds RT2Zn20 (R = La, Pr, T = Ru, Ir)

Electrical resistivity ρ, specific heat C , magnetization M measurements are reported on four compounds, LaRu 2 Zn 20 , PrRu 2 Zn 20 , LaIr 2 Zn 20 , and PrIr 2 Zn 20 , which crystallize in a cubic CeCr 2 Al 20 -type structure. LaRu 2 Zn 20 , LaIr 2 Zn 20 , and PrIr 2 Zn 20 show superconducting transitions at T C = 0.2, 0.6, and ∼0.05 K, respectively, whereas PrRu 2 Zn 20 remains a normal state down to 0.04 K. This is the first observation of superconductivity in the family of RT 2 X 20 (T = transition metal; X = Al and Zn). Furthermore, structural phase transitions manifest themselves at T s = 150, 138, and 200 K for LaRu 2 Zn 20 , PrRu 2 Zn 20 , and LaIr 2 Zn 20 , respectively. No magnetic transition is found in PrRu 2 Zn 20 and PrIr 2 Zn 20 down to 1.8 K. On cooling PrIr 2 Zn 20 below 2 K, the specific heat divided by temperature, C / T , continuously increases and reaches 5 J/(K 2 ·mol) at 0.4 K, suggesting that Pr 4 f 2 electrons are involved in the heavy-fermion state, as observed in a related compo...

BaFeO3: A Ferromagnetic Iron Oxide

Magnetic attraction: The cubic perovskite BaFeO(3) (see picture, Ba blue, Fe brown, O white), which is obtained by a low-temperature reaction using ozone as an oxidant, exhibits ferromagnetism with a fairly large moment of 3.5 μ(B) per Fe ion above a small critical field of approximately 0.3 T. This specific ferromagnetism is attributed to the enhancement of O→Fe charge transfer that arises from deepening of the Fe(4+) d levels.

Superconductivity in a pyrochlore-related oxide KOs2O6

We report the discovery of a new superconductor KOs2O6. The compound crystallizes in a defect pyrochlore structure, where Os atoms form a corner-sharing tetrahedral network called the pyrochlore lattice. Resistivity and magnetic susceptibility measurements on a polycrystalline sample provide evidence of bulk superconductivity with Tc = 9.6?K.

Present Status of the NIMS Contract Beamline BL15XU at SPring-8

The revolver undulator beamline BL15XU at SPring‐8, which is the contract beamline of National Institute for Materials Science (NIMS), was established for materials science using soft‐and‐hard X‐ray photoelectron spectroscopy (XPS) and high‐resolution powder X‐ray diffraction (XRD). We have performed beamline reconstruction for further developments of the experiments in the research field of materials science. The flat double‐crystal monochromator (DCM) with liquid nitrogen cooling, X‐ray total reflection double‐mirror system with (+,−) geometry, and high‐energy‐resolution channel‐cut monochromator have been installed into the beamline. The refined beamline provides monochromatic X‐rays from 2 to 36 keV. The improvement of the photon flux density at the XRD and XPS experimental stations was confirmed. The photon flux was estimated to be several 1012 photons/sec with ΔE/E of ∼10−4.

Synthesis and properties of well-crystallized layered rare-earth hydroxide nitrates from homogeneous precipitation.

We report the synthesis and characteristics of a rare-earth based layered family, Ln(8)(OH)(20)(NO(3))(4) x nH(2)O with Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y, synthesized through homogeneous precipitation of Ln(NO(3))(3) x xH(2)O with hexamethylenetetramine. The products were uniform and of high crystallinity. Their morphology gradually changed from elongated hexagon (Sm, Eu, Gd) and hexagon (Tb, Dy) to rhombus (Ho, Er, Tm). Selected area electron diffraction revealed that the in-plane structure resembled that of the chloride counterpart, Ln(8)(OH)(20)Cl(4) x mH(2)O. Unit cell dimensions of the host layer, a and b, decreased with contracting size of lanthanide ions, whereas no such trend was observed for the interlamellar distance, c/2, which is dominated by hydration degree. Stability of the samples with temperature and relative humidity (RH) was examined. At high temperature or low RHs, hydrated water molecules could be removed, which afforded a phase with a basal decrease of approximately 0.6 A. The transition was reversible as revealed by an in situ powder X-ray diffraction study, but a RH hysteresis exists. The reversibility increased with an increase in atomic number or layer charge density. Nitrate anions of both phases could be quantitatively exchanged by other anions under ambient conditions.