Massive hydration-driven swelling of layered perovskite niobate crystals in aqueous solutions of organo-ammonium bases.

Osmotic swelling behaviors in layered perovskite niobate were examined in aqueous solutions containing three types of amine-related agents including quaternary ammonium hydroxides and tertiary aminoethanol. Platelet microcrystals of a protonated layered perovskite niobate, HCa2Nb3O10·1.5H2O, were found to show enormous swelling in the aqueous solutions, which was clearly recognized by the noticeable expansion of the sample volume over 100-fold. Optical microscopy observations revealed that the crystals underwent accordion-like elongation in the layer-stacking direction up to several ten-fold the initial thickness. Small-angle X-ray scattering measurements of swollen samples indicate the expansion of interlayer separation ranging from ∼20 nm to over 100 nm, which is primarily governed by the concentrations of the amine-related agents. The magnitudes of the interlayer separation were comparable to those of the macroscopic swelling. The degree of swelling was progressively suppressed with further increasing concentration, and this suppression trend was related to the amines.

Accordion-like swelling of layered perovskite crystals via massive permeation of aqueous solutions into 2D oxide galleries.

Platelet crystals of a layered perovskite showed massive accordion-like swelling in a tetrabutylammonium hydroxide solution. The permeation of the solution induced the huge expansion of the interlayer spacing as well as the crystal thickness up to 50-fold, leading to a very high water content of >90 wt%.

Efficient photoinduced charge accumulation in reduced graphene oxide coupled with titania nanosheets to show highly enhanced and persistent conductance.

Tuning of the electrical properties of graphene via photoexcitation of a heteroassembled material has started to attract attention for electronic and optoelectronic applications. Actually photoinduced carrier doping from the hexagonal boron nitride (h-BN) substrate greatly modulated the transport property of the top layer graphene, showing promising potential for this approach. However, for practical applications, the large scale production of this two-dimensional heterostructure is needed. Here, a superlattice film constructed from reduced graphene oxide (rGO) and photoactive titania nanosheets (Ti0.87O2(0.52-)) was employed as a channel to construct a field effect transistor (FET) device, and its UV light response on the electrical transport property was examined. The UV light illumination induced significant improvement of the electrical conductance by ∼7 times on the basis of simultaneous enhancements of the electron carrier concentration and its mobility in rGO. Furthermore, the polarity of the FET response changed from ambipolar to n-type unipolar. Such modulated properties persisted in vacuum even after the UV light was turned off. These interesting behaviors may be explained in terms of photomodulation effects from Ti0.87O2(0.52-) nanosheets. The photoexcited electrons in Ti0.87O2(0.52-) are injected into rGO to increase the electron carrier concentration as high as 7.6×10(13) cm(-2). On the other hand, the holes are likely trapped in the Ti0.87O2(0.52-) nanosheets. These photocarriers undergo reduction and oxidation of oxygen and water molecules adsorbed in the film, respectively, which act as carrier scattering centers, contributing to the enhancement of the carrier mobility. Since the film likely contains more water molecules than oxygen, upon extinction of UV light, a major portion of electrons (∼80% of the concentration at the UV off) survives in rGO, showing the highly enhanced conductance for days. This surpassing photomodulated FET response and its persistency observed in the present superlattice system of rGO/Ti0.87O2(0.52-) are noteworthy compared with previous studies such as the device with a heteroassembly of graphene/h-BN.

Tuning the surface charge of 2D oxide nanosheets and the bulk-scale production of superlatticelike composites.

The surface charge of various anionic unilamellar nanosheets, such as graphene oxide (GO), Ti0.87O2(0.52-), and Ca2Nb3O10(-) nanosheets, has been successfully modified to be positive by interaction with polycations while maintaining a monodispersed state. A dilute anionic nanosheet suspension was slowly added dropwise into an aqueous solution of high molecular weight polycations, which attach on the surface of the anionic nanosheets via electrostatic interaction. Surface modification and transformation to positively charged nanosheets were confirmed by various characterizations including atomic force microscopy and zeta potential measurements. Because the sizes of the polycations used are much larger than the nanosheets, the polymer chains may run off the nanosheet edges and fold to the fronts of the nanosheets, which could be a reason for the continued dispersion of the modified nanosheets in the suspension. By slowly adding a suspension of polycation-modified nanosheets and pristine anionic nanosheet dropwise into water under suitable conditions, a superlatticelike heteroassembly can be readily produced. Characterizations including transmission electron microscopy and X-ray diffraction measurements provide evidence for the formation of the alternately stacked structures. This approach enables the combination of various pairs of anionic nanosheets with different functionalities, providing a new opportunity for the creation of unique bulk-scale functional materials and their applications.

Superlattice assembly of graphene oxide (GO) and titania nanosheets: fabrication, in situ photocatalytic reduction of GO and highly improved carrier transport.

Two different kinds of two-dimensional (2D) materials, graphene oxide (GO) and titanium oxide nanosheets (Ti0.87O2(0.52-)), were self-assembled layer-by-layer using a polycation as a linker into a superlattice film. Successful construction of an alternate molecular assembly was confirmed by atomic force microscopy and UV-visible absorption spectroscopy as well as X-ray diffraction analysis. Exposure of the resulting film to UV light effectively promoted photocatalytic reduction of GO as well as decomposition of the polycation, which are due to their intimate molecular-level contact. The reduction completed within 3 hours, bringing about a decrease of the sheet resistance by ∼10(6). This process provides a clean and mild route to reduced graphene oxide (rGO), showing advantages over other chemical and thermal reduction processes. A field-effect-transistor device was fabricated using the resulting superlattice assembly of rGO/Ti0.87O2(0.52-) as a channel material. The rGO in the film was found to work as a unipolar n-type conductor, which is in contrast to ambipolar or unipolar p-type behavior mostly reported for rGO films. This unique property may be associated with the electron doping effect from Ti0.87O2(0.52-) nanosheets. A significant improvement in the conductance and electron carrier mobility by more than one order of magnitude was revealed, which may be accounted for by the heteroassembly with Ti0.87(0.52-) nanosheets with a high dielectric constant as well as the better 2D structure of rGO produced via the soft photocatalytic reduction.

Partial alkali-metal ion extraction from K0.8(Li0.27Ti1.73)O4 using PTFE as an extraction reagent.

The alkali-metal ion extraction ability of an inert material, polytetrafluoroethylene (PTFE; empirical formula CF2), was clarified by characterizing a partially alkali-metal ion-extracted layered compound, K0.8(Li0.27Ti1.73)O4. Washing K0.8(Li0.27Ti1.73)O4 in water extracts only 44% of the interlayer K(+) and no intralayer Li(+); on the other hand, 53% of the interlayer K(+) and approximately 10% of the intralayer Li(+) ions were extracted from K0.8(Li0.27Ti1.73)O4 by the reaction with PTFE at 350 °C under flowing Ar. A systematic decrease in the lattice parameters a and c along the intralayer directions and an increase in b along the interlayer direction were observed, consistent with the alkali-metal ion deintercalation amount as a function of the reaction temperatures and the reacted PTFE amounts. After the reaction with K0.8(Li0.27Ti1.73)O4 : CF2 = 1 : 0.6 in mol, the lattice parameter b increased to 1.5607(3) nm from 1.5522(2) of the pristine K0.8(Li0.27Ti1.73)O4, and this change in the lattice parameter was approximately one order of magnitude larger than those in a and c.

Soft-chemical exfoliation of RbSrNb2O6F into homogeneously unilamellar oxyfluoride nanosheets.

Interlayer Rb(+) of the perovskite-type layered oxyfluoride RbSrNb(2)O(6)F was ion-exchanged with H(+), and the protonated phase was reacted with aqueous solution of tetrabutylammonium hydroxide to exfoliate it into nanosheets. The resulting nanosheet suspension exhibits Tyndall scattering of a laser beam, indicating its colloidal nature. Elemental composition of the nanosheet was estimated as Sr(0.98)Nb(2)O(6)F(0.97)(δ-), which was quite close to that of the layer unit of the precursor. The homogeneously unilamellar nature of this nanosheet was confirmed by atomic force and transmission electron microscopy observations and X-ray scattering results. The optical absorption edge of the nanosheet suspension was observed around at 293 nm, and two well-defined peaks with their maxima at 229 and 278 nm were observed. Furthermore, the aqueous suspension of the nanosheet exhibits fluorescence emission in the UV-blue region. These properties of the oxyfluoride nanosheets are quite different from those of its oxide analogues without F(-), such as LnNb(2)O(7)(-) nanosheets (Ln = La(3+), Eu(3+), Sm(3+)), suggesting that anion-site replacement of oxide nanosheets can be utilized to optimize or induce various properties.

Exploration of mid-temperature alkali-metal-ion extraction route using PTFE (AEP): transformation of α-NaFeO2-type layered oxides into rutile-type binary oxides.

Alkali-metal-ion extraction reactions using poly(tetrafluoroethylene) (PTFE; AEP reactions) were performed on two kinds of α-NaFeO(2)-type layered compounds: Na(0.68)(Li(0.68/3)Ti(1-0.68/3))O(2) and K(0.70)(Li(0.70/3)Sn(1-0.70/3))O(2). At 400 °C in flowing argon, these layered compounds were reacted with PTFE. By these reactions, alkali-metal ions in the layered compounds were successfully extracted, and TiO(2) and SnO(2) with rutile-type structure were formed. The structural similarity between the alkali-metal-ion-extracted layered compounds and the binary metal oxide products in these unique alkali-metal-ion extraction reactions was interpreted in terms of their interatomic distance distribution by atomic pair distribution function analysis. The results of this study indicate that PTFE is an effective agent to extract alkali-metal ions from layered compounds, and AEP reaction is not limited to the previously reported γ-FeOOH-type layered titania K(0.8)(Li(0.27)Ti(1.73))O(4), but is also applicable to other layered titania and other non-titanium-based layered metal oxides. Therefore, it was clarified that AEP reactions are widely applicable routes to prepare various compounds, including those that are difficult to synthesize by other reactions.

A bona fide two-dimensional percolation model: an insight into the optimum photoactivator concentration in La2/3-x Eu x Ta2O7 nanosheets.

La-Eu solid solution nanosheets La2/3-x Eu x Ta2O7 have been synthesized, and their photoluminescence properties have been investigated. La2/3-x Eu x Ta2O7 nanosheets were prepared from layered perovskite compounds Li2La2/3-x Eu x Ta2O7 as the precursors by soft chemical exfoliation reactions. Both the precursors and the exfoliated nanosheets exhibit a decrease in intralayer lattice parameters as the Eu contents increase. However, there is a discontinuity in this trend between the nominal Eu content ranges x≤ 0.3 and x ≥ 0.4. This discontinuity is attributed to the difference in degree of TaO6 octahedra tilting for the La- and Eu-rich phases. La2/3-x Eu x Ta2O7 nanosheets exhibit red emission, characteristic of the f-f transitions in Eu3+ photoactivators. The photoluminescence emission can be obtained from both host and direct photoactivator excitation. However, photoluminescence emission through host excitation is much more dominant than that through direct photoactivator excitation, and this behavior is consistent with that of all the other rare-earth photoactivated nanosheets reported previously. The absolute photoluminescence quantum efficiency of the La2/3-x Eu x Ta2O7 nanosheets increases as the experimentally determined Eu contents increase up to x=0.45 and decrease above it. This result is in good agreement with the optimum photoactivator concentration expected from the percolation theory. These solid solution La2/3-x Eu x Ta2O7 nanosheets are excellent models for validating the theory of optimum photoactivator concentration in the truly two-dimensional photoactivator matrix.

Engineered interfaces of artificial perovskite oxide superlattices via nanosheet deposition process.

Combining different materials into desired superlattice structures can produce new electronic states at the interface and the opportunity to create artificial materials with novel properties. Here we introduce a new, rather unexpected, and yet simple way to such a superlattice assembly of perovskite oxides: in the Dion-Jacobson phase, a model system of layered perovskites, high-quality bicolor perovskite superlattices (LaNb(2)O(7))(nL)(Ca(2)Nb(3)O(10))(nC) are successfully fabricated by a layer-by-layer assembly using two different perovskite nanosheets (LaNb(2)O(7) and Ca(2)Nb(3)O(10)) as a building block. The artificially fabricated (LaNb(2)O(7)/Ca(2)Nb(3)O(10)) superlattices are structurally unique, which is not feasible to create in the bulk form. By such an artificial structuring, we found that (LaNb(2)O(7)/Ca(2)Nb(3)O(10)) superlattices possess a new form of interface coupling, which gives rise to ferroelectricity.

An alkali-metal ion extracted layered compound as a template for a metastable phase synthesis in a low-temperature solid-state reaction: preparation of brookite from K0.8Ti1.73Li0.27O4.

We have designed a new approach to synthesize brookite, i.e., to extract alkali-metal ions from K(0.8)Ti(1.73)Li(0.27)O(4) (KTLO) and to apply simultaneous heat treatment to the remaining lepidocrocite-type layers of TiO(6) octahedra. For the alkali-metal ion extraction and the simultaneous heat treatment, KTLO was heated at 400 degrees C with polytetrafluoroethylene (PTFE) in flowing Ar. PTFE has been found to be an effective agent to extract strongly electropositive alkali-metal ions from KTLO because of the strong electronegativity of F as its component. The product of this reaction consists of a mixture of brookite, K(2)CO(3), LiF, and PTFE derivatives, indicating the complete extraction of K(+) and Li(+) from KTLO and formation of brookite from the lepidocrocite-type layer of TiO(6) octahedra as a template. This brookite has a partial replacement of O(2-) with F(-) and/or slight oxygen deficiency; thus, its color is light-bluish gray. Fully oxidized brookite formation and complete decomposition of PTFE derivatives have been achieved by further heating in flowing air, and coproduced alkali-metal salts have been removed by washing in water. Powder X-ray diffraction, Raman spectroscopy, and chemical analysis results have confirmed that the final brookite product treated at 600 degrees C is single phase, and it is white. The method to extract alkali-metal ions from a crystalline material using PTFE is drastically different from the common methods such as soft-chemical and electrochemical reactions. It is likely that this new synthetic approach is applicable to other layered systems to prepare a diverse family of compounds, including novel metastable ones.

Synthesis of a solid solution series of layered Eu(x)Gd(1-x)(OH)2.5Cl0.5 x 0.9 H2O and its transformation into (Eu(x)Gd(1-x))2O3 with enhanced photoluminescence properties.

The synthesis of a series of new layered rare-earth hydroxide solid solutions and their transformation into (Eu(x)Gd(1-x))(2)O(3) crystallites are described. Highly crystalline platelets of Eu(x)Gd(1-x)(OH)(2.5)Cl(0.5) x 0.9 H(2)O solid solutions with various Eu(3+)/Gd(3+) ratios were prepared through a homogeneous precipitation method. The hydroxide solid-solution samples exhibited characteristic Eu(3+) photoluminescence properties through the energy transfer from Gd(3+) to Eu(3+) and the self-excitation of Eu(3+). Cubic (Eu(x)Gd(1-x))(2)O(3) crystallites were obtained via quasi-topotactic transformation of Eu(x)Gd(1-x)(OH)(2.5)Cl(0.5) x 0.9 H(2)O solid solutions above 800 degrees C. The as-transformed cubic (Eu(x)Gd(1-x))(2)O(3) crystallites well retained the original platelet morphology and single crystalline nature, and exhibited greatly enhanced photoluminescence properties with respect to the precursor hydroxides. The Eu(3+) content of 0.05 in the cubic (Eu(x)Gd(1-x))(2)O(3) gave a maximum luminescence intensity, which is comparable with that of a commercial Y(2)O(3):Eu phosphor.

Oriented monolayer film of Gd2O3:0.05 Eu crystallites: quasi-topotactic transformation of the hydroxide film and drastic enhancement of photoluminescence properties.

Caught on film: A semitransparent and intensely luminescent monolayer film of oriented Gd(2)O(3):0.05 Eu platelet crystallites is fabricated by annealing the precursor hydroxide film (see scheme). The photoluminescence properties of the as-transformed film are greatly improved over those of the hydroxide film, and are much more pronounced than those of the corresponding Gd(2)O(3):0.05 Eu powder.

Oriented films of layered rare-earth hydroxide crystallites self-assembled at the hexane/water interface.

Layered rare-earth hydroxide crystallites self-assembled at the hexane/water interface were transferred to various substrates to form a monolayer film, which exhibited photoluminescence properties and ion-exchange ability.

Chemistry of layered d-metal pnictide oxides and their potential as candidates for new superconductors.

Layered d-metal pnictide oxides are a unique class of compounds which consist of characteristic d-metal pnictide layers and metal oxide layers. More than 100 of these layered compounds, including the recently discovered Fe-based superconducting pnictide oxides, can be classified into nine structure types. These structure types and the chemical and physical properties of the characteristic d-metal pnictide layers and metal oxide layers of the layered d-metal pnictide oxides are reviewed and discussed. Furthermore, possible approaches to design new superconductors based on these layered d-metal pnictide oxides are proposed.

NaCl/KCl flux single crystal growth and crystal structure of the new quaternary mixed-metal pnictide: BaCuZn3As3.

Synthesis and crystal structure of a new compound, BaCuZn(3)As(3), are reported. Single crystals of BaCuZn(3)As(3) are synthesized via NaCl/KCl flux reaction in a sealed fused silica ampule. Its elemental composition has been determined to be Ba/Cu/Zn/As = 1.03(4):1(0):2.91(6):2.98(3), suggesting BaCuZn(3)As(3) as the chemical formula. The structure of BaCuZn(3)As(3) has been determined by X-ray diffraction. It crystallizes in the orthorhombic Cmcm space group with a = 4.2277(3) A, b = 12.970(1) A, and c = 12.011(1) A at T = 90.7 K, and it exhibits a columnar structure along the a-axis. This structure is isotypic to beta-BaCu(4)S(3) but highly distorted. beta-BaCu(4)S(3) is considered to be a layered structure whereas BaCuZn(3)As(3) is a three-dimensional network.

Formation of a one-dimensional array of oxygen in a microporous metal-organic solid.

We report the direct observation of dioxygen molecules physisorbed in the nanochannels of a microporous copper coordination polymer by the MEM (maximum entropy method)/Rietveld method, using in situ high-resolution synchrotron x-ray powder diffraction measurements. The obtained MEM electron density revealed that van der Waals dimers of physisorbed O2 locate in the middle of nanochannels and form a one-dimensional ladder structure aligned to the host channel structure. The observed O-O stretching Raman band and magnetic susceptibilities are characteristic of the confined O2 molecules in one-dimensional nanochannels of CPL-1 (coordination polymer 1 with pillared layer structure).