Bi4AO6Cl2 (A = Ba, Sr, Ca) with Double and Triple Fluorite Layers for Visible-Light Water Splitting.

Layered oxyhalides containing double or triple fluorite layers are promising visible-light-responsive water-splitting photocatalysts with unique band structures. Herein, we report on the synthesis, structure, and photocatalytic property of Bi4BaO6Cl2 (I4/mmm) with alternating double (Bi2O2) and triple (Bi2BaO4) fluorite layers, which was extracted from the crystallographic database on the basis of Madelung potential calculations. Rietveld refinements from powder X-ray and neutron diffraction data revealed the presence of cationic disorder between Bi2O2 and Bi2BaO4 layers, leading to electrostatic stabilization. DFT calculations suggested that photogenerated electrons and holes flow through the double and triple layers, respectively, which may suppress electron-hole recombination. We expanded this double-triple system to include Bi4CaO6Cl2 and Bi4SrO6Cl2 with orthorhombic distortions and different degrees of cationic disorder, which allow band gap tuning. All the double-triple compounds Bi4AO6Cl2 showed stable water-splitting photocatalysis in the presence of a sacrificial reagent.

Encapsulation kinetics and dynamics of carbon monoxide in clathrate hydrate.

Carbon monoxide clathrate hydrate is a potentially important constituent in the solar system. In contrast to the well-established relation between the size of gaseous molecule and hydrate structure, previous work showed that carbon monoxide molecules preferentially form structure-I rather than structure-II gas hydrate. Resolving this discrepancy is fundamentally important to understanding clathrate formation, structure stabilization and the role the dipole moment/molecular polarizability plays in these processes. Here we report the synthesis of structure-II carbon monoxide hydrate under moderate high-pressure/low-temperature conditions. We demonstrate that the relative stability between structure-I and structure-II hydrates is primarily determined by kinetically controlled cage filling and associated binding energies. Within hexakaidecahedral cage, molecular dynamic simulations of density distributions reveal eight low-energy wells forming a cubic geometry in favour of the occupancy of carbon monoxide molecules, suggesting that the carbon monoxide-water and carbon monoxide-carbon monoxide interactions with adjacent cages provide a significant source of stability for the structure-II clathrate framework.

Experimental visualization of lithium conduction pathways in garnet-type Li7La3Zr2O12.

The evolution of the Li-ion displacements in the 3D interstitial pathways of the cubic garnet-type Li(7)La(3)Zr(2)O(12), cubic Li(7)La(3)Zr(2)O(12), was investigated with high-temperature neutron diffraction (HTND) from RT to 600 °C; the maximum-entropy method (MEM) was applied to estimate the Li nuclear-density distribution. Temperature-driven Li displacements were observed; the displacements indicate that the conduction pathways in the garnet framework are restricted to diffusion through the tetrahedral sites of the interstitial space.

Dramatic structural rearrangements in porous coordination networks.

With the use of ab initio X-ray powder diffraction, a family of isostructural crystalline porous coordination networks, [(ZnX(2))(3)(TPT)(2)](n)· (solvent) (X = I, Br, Cl), has been studied at elevated temperatures of 573-723 K. Upon heating, all three networks exhibited crystalline-to-amorphous-to-crystalline (CAC) phase transformations to three new networks, [(ZnI(2))(3)(TPT)(2)](n), [(ZnBr(2))(3)(TPT)(2)](n)·(H(2)O) and [(ZnBr(2))(µ-Br)(ZnBr)(TPT)](n), and [(ZnCl(2))(µ-Cl)(ZnCl)(TPT)](n), respectively. A set of control experiments was used to obtain detailed mechanistic aspects of the CAC transformations. We demonstrate how bonds are broken and formed in these significant molecular rearrangements and how the initial arrangement plays a crucial role in the formation of the new networks after the CAC transformations. The structural information in the amorphous phase is retained and passed from a metastable to a more stable crystal, thus, reinforcing the notion that coordination networks are flexible and chemically active.

Synthesis and crystal structure of a layered silicate HUS-1 with a halved sodalite-cage topology.

A new layered silicate, HUS-1, was synthesized by hydrothermal synthesis using decomposed FAU- and *BEA-type zeolites as nanosized silica parts. Structural analyses by X-ray powder diffractometry and solid-state magic-angle-spinning (MAS) NMR spectroscopy revealed that HUS-1 has a layered structure containing a silicate layer per unit cell along a stacking direction. Its framework topology is similar to that of SOD-type zeolites and consists of a halved sodalite cage, which includes four- and six-membered Si rings. Structure refinement by the Rietveld method showed that tetramethylammonium (TMA) ions used as a structure-directing agent (SDA) were incorporated into the interlayer. The four methyl groups of the TMA molecule were located orderly in a hemispherical cage in the silicate layer, which suggests restraint of molecular motion. The interlayer distance is estimated at about 0.15 nm, which is unusually short in comparison with that in other layered silicates (e.g., ß-HLS or RUB-15) with similar framework topologies. The presence of hydrogen bonding between adjacent terminal O atoms was clearly revealed by the (1)H MAS NMR spectroscopy and by electron-density distribution obtained by the maximum entropy method.

Solid-liquid interface synthesis of microcrystalline porous coordination networks.

Solid-liquid interface synthesis provided a unique way to selectively and efficiently prepare molecular complexes (ML(2)) and metastable porous coordination networks in short crystallization times. In sharp contrast, their solution reactions gave interpenetrated open-framework networks. We succeeded in solving a crystal structure of the metastable network by ab initio powder X-ray analysis.

Formation of a thermally stable, porous coordination network via a crystalline-to-amorphous-to-crystalline phase transition.

A porous coordination network was cleanly obtained after a crystalline-to-amorphous-to-crystalline phase transition, and the crystal structure was unambiguously solved by ab initio powder X-ray diffraction. After the solid-state phase transition, the porous structure was remarkably stable up to 673 K and capable of reabsorbing various guest molecules, such as aromatic solvents and I(2).

General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x 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.

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.

Superconductivity in two-dimensional CoO2 layers.

Since the discovery of high-transition-temperature (high-T(c)) superconductivity in layered copper oxides, many researchers have searched for similar behaviour in other layered metal oxides involving 3d-transition metals, such as cobalt and nickel. Such attempts have so far failed, with the result that the copper oxide layer is thought to be essential for superconductivity. Here we report that Na(x)CoO2*yH2O (x approximately 0.35, y approximately 1.3) is a superconductor with a T(c) of about 5 K. This compound consists of two-dimensional CoO2 layers separated by a thick insulating layer of Na+ ions and H2O molecules. There is a marked resemblance in superconducting properties between the present material and high-T(c) copper oxides, suggesting that the two systems have similar underlying physics.