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Rare earth metal borides have attracted great interest due to their unusual properties, such as superconductivity and f-electron magnetism. A recent discovery attributes the tunability of magnetism in rare earth aluminoborides to the effect of so-called “building defects.” In this paper, we report data for the effect of building defects on the thermal conductivities of α-TmAlB4 single crystals. Building defects reduce the thermal conductivity of α-TmAlB4 by ≈30%. At room temperature, the thermal conductivity of AlB2 is nearly a factor of 5 higher than that of α-TmAlB4. AlB2 single crystals are thermally anisotropic with the c-axis thermal conductivity nearly twice the thermal conductivity of the a-b plane. Temperature dependence of the thermal conductivity near and above room temperature reveals that both electrons and phonons contribute substantially to thermal transport in AlB2 with electrons being the dominant heat carriers.

Rare earth metal borides have attracted great interest due to their unusual properties, such as superconductivity and f-electron magnetism. A recent discovery attributes the tunability of magnetism in rare earth aluminoborides to the effect of so-called "building defects." In this paper, we report data for the effect of building defects on the thermal conductivities of α-TmAlB4 single crystals. Building defects reduce the thermal conductivity of α-TmAlB4 by ≈30%. At room temperature, the thermal conductivity of AlB2 is nearly a factor of 5 higher than that of α-TmAlB4. AlB2 single crystals are thermally anisotropic with the c-axis thermal conductivity nearly twice the thermal conductivity of the a-b plane. Temperature dependence of the thermal conductivity near and above room temperature reveals that both electrons and phonons contribute substantially to thermal transport in AlB2 with electrons being the dominant heat carriers. [ABSTRACT FROM AUTHOR]

Theoretically predicted materials are often synthesized in low yields, and unexpected relationships are often encountered between the target materials and byproducts. Recently, two-dimensional boron materials proposed on the basis of model simulations and first principles calculations and possessing abundant atomic structures have attracted considerable interest. Borophane or the hydrogen boride (HB) sheet has been predicted to be the Dirac nodal semimetal when it has a boron network of nonsymmorphic symmetry. Upgrading the standard method, we fabricated freestanding HB sheets possessing either an apparent Fermi edge, reduced spectral weight, or a Fermi-level energy gap, as confirmed by using microbeam photoemission spectroscopy. The gapless electronic structures were correlated with terminal B-H bonds at the sheet edges, indicating the electronic modification of the porous structure as directly microscopically observed. The gapped or insulating sheet was fabricated via oxidation. This research provides methods for regulating the structural morphology and electronic states of HB sheets during synthesis.

The water oxidation reaction is a rate-determining step in solar water splitting. The number of surviving photoexcited holes is one of the most influencing factors affecting the photoelectrochemical water oxidation efficiency of photocatalysts. The solar-to-hydrogen energy conversion efficiency of BaTaO 2 N is still far below the benchmark efficiency set for practical applications, notwithstanding its potential as a 600 nm-class photocatalyst in solar water splitting. To improve its efficiency in photoelectrochemical water splitting, this study offers a straightforward route to develop photocatalytic materials based on the combination of BaTaO 2 N and carbonaceous materials with different dimensions. The impact of diverse carbonaceous materials, such as fullerene, g-C 3 N 4 , graphene, carbon nanohorns, and carbon nanotubes, on the photoelectrochemical behavior of BaTaO 2 N has been examined. Notably, the use of graphene and g-C 3 N 4 remarkably improves the photoelectrochemical performance of the composite photocatalysts through a higher photocurrent and acting as electron reservoirs. Consequently, a marked reduction in recombination rates, even at low overpotentials, leads to a higher accumulation of photoexcited holes, resulting in 2.6- and 1.7-fold increased BaTaO 2 N photocurrent densities using graphene and g-C 3 N 4 , respectively. The observed trends in the dark for the oxygen reduction reaction (ORR) potential align with the increase in the photocurrent density, revealing a good correlation between opposite phenomena. Importantly, the enhancement observed implies an underlying accumulation phenomenon. The verification of this concept lies in the evidence provided by oxygen reduction and is in line with photoredox flux matching during photocatalysis. This research underscores the intricate interplay between carbonaceous materials and oxynitride photocatalysts, offering a strategic approach to enhancing various photocatalytic capabilities., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The structural parameters of yttrium chromium tetra-boride YCrB 4 were refined based on single-crystal X-ray diffraction data. YCrB 4 is ortho-rhom-bic, having a space group of type Pbam (No. 55) and with lattice parameters of a = 5.9425 (2), b = 11.4831 (4), c = 3.4643 (1) Å. The Y and Cr atoms are located at Wyckoff 4 h sites ( x , y , 0) and B atoms at the Wyckoff 4 g sites ( x , y , 1/2). The first structural investigation of YCrB 4 was performed using a single crystalline sample [Kuz'ma, (1970 ▸). Kristallografiya . 15 , 372-374]. The present study successfully refined all the positional and atomic displacement parameters of the Y, Cr, and B atoms., (© Tokuda et al. 2023.)

This paper proposes a method that provides a phase image related to the demagnetization field (Hd) within a thin-foil permanent magnet using electron holography. The observation of Hd remains a significant challenge because electron holography in principle allows only imaging of the magnetic flux density (B), which is a mixture of the contributions from magnetization (M), stray magnetic field (Hs) outside of the specimen and Hd inside of the specimen. The phase map approximating Hd, which was determined by processing of the electron holography observation from a Nd2Fe14B single-crystalline specimen, showed a good agreement with the prediction by micromagnetic theory. With respect to permanent magnets, this method can be applied to examinations about the coercivity mechanism, which is sensitive to the demagnetization field. Graphical Abstract., (© The Author(s) 2022. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

We present an enhanced method for synthesizing sheets of borophane. Despite the challenges associated with low efficiency, we discovered that incorporating hydrochloric acid into the ion-exchange reaction significantly improved the production yield from 20% to over 50%. After a thorough examination of the reaction, we gained insight into the underlying mechanisms and found that the use of hydrochloric acid provides two key benefits: accelerated production of borophene and isolation of high-purity products. This method has the potential to pave the way for the production of novel topological 2D materials with potential industrial applications.

A goal in the characterization of supported metal catalysts is to achieve particle-by-particle analysis of the charge state strongly correlated with the catalytic activity. Here, we demonstrate the direct identification of the charge state of individual platinum nanoparticles (NPs) supported on titanium dioxide using ultrahigh sensitivity and precision electron holography. Sophisticated phase-shift analysis for the part of the NPs protruding into the vacuum visualized slight potential changes around individual platinum NPs. The analysis revealed the number (only one to six electrons) and sense (positive or negative) of the charge per platinum NP. The underlying mechanism of platinum charging is explained by the work function differences between platinum and titanium dioxide (depending on the orientation relationship and lattice distortion) and by first-principles calculations in terms of the charge transfer processes.

The use of antiviral drugs has surged as a result of the COVID-19 pandemic, resulting in higher concentrations of these pharmaceuticals in wastewater. The degradation efficiency of antiviral drugs in wastewater treatment plants has been reported to be too low due to their hydrophilic nature, and an additional procedure is usually necessary to degrade them completely. Photocatalysis is regarded as one of the most effective processes to degrade antiviral drugs. The present study aims at synthesizing multiphase photocatalysts by a simple calcination of industrial waste from ammonium molybdate production (WU photocatalysts) and its combination with WO 3 (WW photocatalysts). The X-ray diffraction (XRD) results confirm that the presence of multiple crystalline phases in the synthesized photocatalysts. UV-Vis diffuse reflectance spectra reveal that the synthesized multiphase photocatalysts absorb visible light up to 620 nm. Effects of calcination temperature of industrial waste (550-950 °C) and WO 3 content (0-100%) on photocatalytic activity of multiphase photocatalysts (WU and WW) for efficient removal of SARS-CoV-2 antiviral drugs (lopinavir and ritonavir) in model and real wastewaters are studied. The highest k 1 value is observed for the photocatalytic removal of ritonavir from model wastewater using WW4 (35.64 ×10 -2 min -1 ). The multiphase photocatalysts exhibit 95% efficiency in the photocatalytic removal of ritonavir within 15 of visible light irradiation. In contrast, 60 min of visible light irradiation is necessary to achieve 95% efficiency in the photocatalytic removal of lopinavir. The ecotoxicity test using zebrafish (Danio rerio) embryos shows no toxicity for photocatalytically treated ritonavir-containing wastewater, and the contrary trend is observed for photocatalytically treated lopinavir-containing wastewater. The synthesized multiphase photocatalysts can be tested and applied for efficient degradation of other SARS-CoV-2 antiviral drugs in wastewater in the future., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The crystal structures of the rare-earth ( RE ) trirhodium diborides praseo-dymium trirhodium diboride, PrRh 3 B 2 , neodymium trirhodium diboride, NdRh 3 B 2 , and samarium trirhodium diboride, SmRh 3 B 2 , were refined on the basis of single-crystal X-ray diffraction data. The crystal chemistry of RE Rh 3 B 2 ( RE : Pr, Nd, and Sm) compounds has previously been analyzed mainly on the basis of powder samples [Ku et al. (1980 ▸). Solid State Commun . 35 , 91-96], and no structural investigation by single-crystal X-ray diffraction has been reported so far. The crystal structures of the three hexa-gonal RE Rh 3 B 2 compounds are isotypic with that of CeRh 3 B 2 ; RE , Rh and B sites are situated on special positions with site symmetry 6/ mmm (Wyckoff position 1 a ), mmm (3 g ) and m 2 (2 c ), respectively. In comparison with the previous powder X-ray study of hexa-gonal RE Rh 3 B 2 , the present redetermination against single-crystal X-ray data has allowed for the modeling of all atoms with anisotropic displacement parameters (ADPs). The ADPs of the Rh atom in each of the structures result in an elongated displacement ellipsoid in the direction of the stacking of the Rh kagomé-type layer. The features of obtained ADPs of atoms are discussed in relation to RE Rh 3 B 2 -type and analogous structures., (© Tokuda et al. 2022.)

A single-phase sample of α' (O'3)-type layered sodium cobalt oxide Na x CoO 2 (x ∼ 0.78) was prepared and its incommensurately modulated crystal structure was analyzed using the (3+1)-dimensional superspace approach to the powder neutron diffraction data. The crystal structure of the cobaltate is accurately described based on the superspace group C2/m(α0γ)00, wherein the positions of Na atoms are most significantly modulated in the monoclinic a direction to form an ordered arrangement. Such a displacive modulation causes a quasi-periodic shift of Na atoms from the centers of the NaO 6 polyhedra between undulated CoO 2 sheets, changing the form of the NaO 6 polyhedron from an octahedral coordination (O) to a trigonal prismatic (P) one, via an intermediate capped trigonal prismatic NaO 7 coordination (C). At the positions where the Na atoms are most significantly shifted, the neighboring Na atoms are located at almost touching distances. However, the occupation factor of Na atoms becomes zero at such positions, yielding Na-deficient sites V Na , sandwiched either between C and P, or C and C-type polyhedra.

In this study, elsmoreite/tungsten oxide is used to form a heterojunction with ZnS-containing industrial waste. The effect of the elsmoreite/tungsten oxide content on photocatalytic activity of ZnS using the different ratios of ZnS:Na 2 WO 4 in the synthesis solution is estimated. The initial ZnS:Na 2 WO 4 ratio leads to the formation of hexagonal WO 3 ∙0.33H 2 O on the surface of ZnS. A further increase in the ZnS:Na 2 WO 4 ratio results in the domination of cubic WO 3 ∙0.5H 2 O over hexagonal WO 3 . The ultraviolet-visible (UV-Vis) diffuse reflectance spectra of elsmoreite/tungsten oxide@ZnS composite photocatalysts show that the absorption onset shifts monotonously towards lower wavelengths from 450 nm to 400 nm. The microrods of hexagonal WO 3 and {111}-truncated submicron-sized crystals of WO 3 ∙0.5H 2 O are grown on the ZnS surface. The transmission electron microscopy (TEM) results confirm the formation of a heterojunction between elsmoreite/tungsten oxide and ZnS. The photocatalytic activities of elsmoreite/tungsten oxide@ZnS composite photocatalysts are evaluated for the degradation of selected pharmaceuticals and personal care products (PPCPs): metoprolol - Mt, triclosan - TCS, and caffeine - CAF both in single and in mixture solutions. The elsmoreite/tungsten oxide@ZnS photocatalysts degrade 50% of Mt, 70% TCS, and 60% CAF in single solution and 35% of Mt, 20% of CAF, and 20% of TCS in mixture solution. Hydrated Mt and TCS are preferably adsorbed on the surface of WO 3 ∙0.5H 2 O (111), and CAF has better affinity to the surface of WO 3 . The elsmoreite/tungsten oxide@ZnS photocatalysts show a good reusability. Hydroxyl radicals ( • OH) and photogenerated holes (h + ) are involved in the photocatalytic removal of Mt, while only h + is involved in the photocatalytic removal of TCS. Interestingly, none of the above-mentioned species is involved in the photocatalytic removal of CAF. Also, nontoxic CAF is mainly degraded into intermediates with higher toxicity. The toxicity of the photocatalytically treated model wastewater in the mixture solution, tested with Vibrio fischeri, is much lower than that in the single solution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Hollandite-type crystals have unique and interesting physical and chemical properties. Here, we report the flux growth of hollandite-type single-crystalline potassium ferrotitanate (KFTO) with faceted surface features from a KCl flux. We varied the flux growth conditions, including the kind of flux, holding temperature, and solute concentration for growing faceted crystallites. KCl was found to be the best flux to grow the single-crystalline KFTO particles, while heating at or above 900°C was needed to yield the KFTO single crystals. The crystal growth was only weakly dependent on the solute concentration. Next, we characterized the grown single crystals and discussed the manner of their growth from the KCl flux. TEM images with clear electron diffraction spots indicated that the KFTO crystals grew along the <001> direction to form microrods ~10 μm in size. DFT calculation results indicated that the surface energy of the (100) face is lower than that of the (001) face. Based on these characterization results, we proposed a possible growth mechanism of the KFTO crystals., (Copyright © 2020 Hayashi, Furui, Shiiba, Yubuta, Sudare, Terashima and Teshima.)

Y x Al y B 14 ceramics are of high interest as high temperature thermoelectric materials with excellent p, n control. In this study, direct synthesis of dense polycrystalline Y x Al y B 14 (x ~0.64, 0.52 ≤ y ≤ 0.67) ceramics was successfully carried out by spark plasma sintering using commercially available precursors. YB 4 , AlB 2 and B powders were reactively sintered with an additive AlF 3 at 1773 K for 5-60 min in reduced Ar atmosphere. The sinterability was remarkably enhanced by liquid phase sintering comparing to conventional synthesis techniques. Phase composition analysis by X-ray diffraction showed that main peaks belong to Y x Al y B 14 with the MgAlB 14 structure type and no peaks of AlF 3 were detected. The thermoelectric behavior was changed from p-type to n-type with increasing Al occupancy. Power factor and ZT values measured in this study were found to be in the same range as the best values previously reported. This original synthesis process is found to be less precursor-consuming as compared to previous synthesis processes, and strikingly, less time-consuming, as the synthesis time, is shortened from 8 h to 5 min for p-type and to 1 h for n-type. The total process time is shortened from ≥3 days to ~4-5 h. This discovery opens the door for more accessible synthesis of complex borides.

Oxygen evolution reaction (OER) catalysts are critical components of photoanodes for photoelectrochemical (PEC) water oxidation. Herein, nanostructured metal boride MB (M = Co, Fe) electrocatalysts, which have been synthesized by a Sn/SnCl 2 redox assisted solid-state method, were integrated with WO 3 thin films to build heterojunction photoanodes. As-obtained MB modified WO 3 photoanodes exhibit enhanced charge carrier transport, amended separation of photogenerated electrons and holes, prolonged hole lifetime and increased charge carrier density. Surface modification of CoB and FeB significantly enhances the photocurrent density of WO 3 photoanodes from 0.53 to 0.83 and 0.85 mA cm -2 , respectively, in transient chronoamperometry (CA) at 1.23 V vs. RHE (V RHE ) under interrupted illumination in 0.1 M Na 2 SO 4 electrolyte (pH 7), corresponding to an increase of 1.6 relative to pristine WO 3 . In contrast, the pristine MB thin film electrodes do not produce noticeable photocurrent during water oxidation. The metal boride catalysts transform in situ to a core-shell structure with a metal boride core and a metal oxide (MO, M = Co, Fe) surface layer. When coupled to WO 3 thin films, the CoB@CoO x nanostructures exhibit a higher catalytic enhancement than corresponding pure cobalt borate (Co-B i ) and cobalt hydroxide (Co(OH) x ) electrocatalysts. Our results emphasize the role of the semiconductor-electrocatalyst interface for photoelectrodes and their high dependency on materials combination.

Low charge separation efficiencies are regarded as obstacles that limit the improvement in the photocatalytic performance of BaTaO 2 N. In this study, we demonstrated that the anisotropic facets ({100} and {110} facets) of BaTaO 2 N for efficient spatial charge separation were successfully constructed using the one-pot flux-assisted nitridation approach. As a result, the photocatalytic activity for H 2 production on BaTaO 2 N with coexposed {100} and {110} facets was nearly 10-fold over that of BaTaO 2 N with only {100} facets and that of the conventional irregularly shaped sample. This finding provides an innovative approach to the development of efficient (oxy)nitride photocatalysts for solar energy conversion.

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work, we demonstrate the direct growth of cubic Li 5 La 3 Nb 2 O 12 crystal layer on the LiCoO 2 substrate through the conversion of ultra-thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with Σ3 (2-1-1) = (1-21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb 2 O 5 thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.

Transition metal (oxy)nitrides with perovskite-type structures have been regarded as one of the promising classes of inorganic semiconductor materials that can be used in solar water splitting systems for the production of hydrogen as a renewable and storable energy carrier. The performance of transition metal (oxy)nitrides in solar water splitting is strongly influenced by the crystal structure-related dynamics of photogenerated charge carriers. Here, we have systematically assessed the influence of A-site cation exchange on the visible-light-induced photocatalytic H 2 and O 2 evolution activities, photoanodic response, and dynamics of photogenerated charge carriers of perovskite-type LnTaON 2 (Ln = La and Pr). The structural refinement results reveal the orthorhombic Imma and Pnma structures for LaTaON 2 and PrTaON 2 , respectively; the latter has a more distorted crystal structure from the ideal cubic perovskite due to the smaller size of Pr 3+ cations. Compared with LaTaON 2 , PrTaON 2 exhibits lower photocatalytic H 2 and O 2 gas evolution activities and photoanodic response owing to an excessive amount of intrinsic defects associated with anionic vacancies and reduced tantalum species stemming from a long high-temperature nitridation process under reductive NH 3 atmosphere. Transient absorption signals evidence the faster decay of photogenerated electrons (holes) in Pt (CoO x )-loaded LaTaON 2 than that in Pt (CoO x )-loaded PrTaON 2 , consistent with the photocatalytic and photoelectrochemical performance of the two photocatalysts. This study suggests that in addition to selecting a suitable A-site cation, it is prerequisite to synthesize LnTaON 2 (Ln = La and Pr) crystals with a low defect density to improve their photo-conversion efficiency for solar water splitting.

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering-that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF 2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique.

The effect of the Ta/Nb ratio in the (111)-layered B-site deficient hexagonal perovskite Ba5Nb4-xTaxO15 (0 ≤ x ≤ 4) crystals grown by a KCl flux method on visible-light-induced photocatalytic water oxidation activity of their oxynitride derivatives BaNb1-xTaxO2N (0 ≤ x ≤ 1) was investigated. The Rietveld refinement of X-ray data revealed that all Ba5Nb4-xTaxO15 samples were well crystallized in the space group P3[combining macron]m1 (no. 164). Phase-pure BaNb1-xTaxO2N (0 ≤ x ≤ 1) porous structures were obtained by nitridation of the flux-grown oxide crystals at 950 °C for 20, 25, 30, 35, and 40 h, respectively. The absorption edge of BaNb1-xTaxO2N (0 ≤ x ≤ 1) was slightly shifted from 720 to 690 nm with the increasing Ta/Nb ratio. The O2 evolution rate gradually progressed and reached the highest value (127.24 μmol in the first 2 h) with the Ta content up to 50 mol% but decreased at 75 and 100 mol% presumably due to the reduced specific surface area and high density of structural defects, such as grain boundaries acting as recombination centers, originated from high-temperature nitridation for prolonged periods. Transient absorption spectroscopy provided evidence for the effect of the Ta/Nb ratio on the behavior and energy states of photogenerated charge carriers, indicating a direct correlation with photocatalytic water oxidation activity of BaNb1-xTaxO2N.

Flux growth is a promising method that allows one to control over the crystalline phase, crystal shape, crystal size, and crystal surface through the selection of a suitable flux. In this work, lanthanum titanate (La2Ti2O7) crystals with different morphologies were grown using the Na2MoO4, K2MoO4, NaCl, and mixed NaCl + K2MoO4 (molar ratio = 3:7) fluxes, and their nitridability to form LaTiO2N crystals under a high-temperature NH3 atmosphere was also investigated. The effects of the solute concentration and cooling rate on the growth of the La2Ti2O7 crystals were also studied. The X-ray diffraction results revealed that the {100} plane was dominant in the La2Ti2O7 platelet crystals grown using the alkali-metal molybdate fluxes. When the solute concentration was increased from 1 to 20 mol %, the average size of the crystals decreased without considerable alteration of the overall crystal morphology. The La2Ti2O7 crystals with the preferred ⟨010⟩ and ⟨001⟩ growth directions along the b and c axes were grown using the Na2MoO4 and K2MoO4 fluxes, respectively. Compared to the Na2MoO4 flux, the K2MoO4 flux did not show a cooling-rate-dependent effect on the growth of the La2Ti2O7 crystals. It was found that conversion of the La2Ti2O7 crystals to the LaTiO2N crystals was strongly dependent on the flux used to grow the precursor La2Ti2O7 crystals. That is, the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes were nearly completely converted into the LaTiO2N crystals, while conversion of the La2Ti2O7 crystals grown using the Na2MoO4 and mixed NaCl + K2MoO4 fluxes to the LaTiO2N crystals seemed to be not completed yet even after nitridation at 950 °C for 15 h using NH3 because of the larger crystal size and the presence of unintentional impurities (sodium and molybdenum from the flux) in the La2Ti2O7 crystal lattice. Nevertheless, the LaTiO2N crystals fabricated by nitriding the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes should be suitable for direct solar water splitting.

We synthesized freestanding bulk three-dimensional nanoporous Si using dealloying in a metallic melt, a top-down process. Using this nanoporous Si, we fabricated negative electrodes with high lithium capacity, nearing their theoretical limits, and greatly extended cycle lifetimes, considerably improving the battery performance compared with those using electrodes made from silicon nanoparticles. By operating the electrodes below the accommodation volume limit of their pores, we prolonged their cycle lifetime.

Unique Ni compound nanocrystals were successfully grown on carbon nanotubes (CNTs) by cooling a mixed chloride flux. Cup-stacked CNTs (CSCNTs) were used as the nanocarbon materials because of their structural features. The grown nanocrystals had a nanosheet structure, which was densely assembled and had a ribbon-like morphology. Therefore, the nanocrystal/CSCNT composites were expected to have a highly active surface area for the catalyst composites. The selected area electron diffraction pattern and the related radial intensity profiles indicated that the grown nanocrystals were Ni(OH)2. When the pristine CSCNTs were used as a starting material, the formation efficiency of the nanocrystal/CSCNT composites decreased because the pristine CSCNTs were not dispersed in the KCl-LiCl flux. Therefore, functionalization of the CSCNTs was carried out with VUV light irradiation. The dispersibility of the VUV light-treated CSCNTs increased in the KCl-LiCl flux in comparison with the pristine CSCNTs because oxygen-containing functional groups, such as -COOH and -CO, were introduced onto the surfaces of the CSCNTs.

Carbon nanotubes (CNTs) are promising catalyst supports for fuel cell applications. Metal oxide/CNT nanocomposites are also being studied for dye-sensitized solar-cell, photocatalyst, and sensor applications. The fabrication of nanocomposites consisting of highly crystalline NbOx nanotubes and cup-stacked carbon nanotubes (CSCNTs) is reported herein. The CSCNTs were selected for the carbon materials because of their distinctive structure. The CSCNTs were photochemically treated with vacuum ultraviolet light, which increased the amount of oxygen-containing functional groups therein. NbOx nanotubes with no defects were successfully prepared with the chemical treatment of highly crystalline, layered, flux-grown K4Nb6O17 crystals. First, K4Nb6O17 crystals were grown from a KCl flux at a holding temperature of 800 degrees C. Next, NbOx nanosheets were prepared from the layered K4Nb6O17 crystals via a two-step exfoliation process, which consists of proton exchange in an acid solution and intercalation of the tetrabutylammonium ions. The NbOx nanosheets were rolled up into nanotubes with diameters of about 20 nm and lengths of 100-500 nm on the surfaces of the CSCNTs; thus, unique and complex NbOx/CSCNT nanocomposites were successfully fabricated.

A dry process using VUV light was confirmed as a novel technique to attach functional groups onto cup-stacked carbon nanotubes and to develop their isolation in a water system without the use of dispersing agents.

We report measurements and analyses of resistivity, thermopower and the Hall coefficient of single-crystalline samples of the layered Rh oxide K(0.49)RhO(2). The resistivity is proportional to the square of the temperature up to 300 K, and the thermopower is proportional to the temperature up to 140 K. The Hall coefficient increases linearly with the temperature above 100 K, which is ascribed to the triangular network of Rh in this compound. The different transport properties between Na(x)CoO(2) and K(0.49)RhO(2) are discussed on the basis of the different bandwidth between Co and Rh evaluated from the magnetotransport.

We have examined the structure of a U(2)IrSi(3) compound exhibiting ferromagnetic cluster glass behaviour by means of electron diffraction observation and high-resolution electron microscopy. The structure of U(2)IrSi(3) has been proposed as a new one of the U(2)RuSi(3)-type with a short-range ordered double stacking sequence of the U(2)RuSi(3)-type structure along the c-axis, and long-range ordered atomic arrangements in the a-b plane. The calculated patterns reproduce the characteristic features of observed electron patterns well. The Fourier-filtered high-resolution image clearly exhibits a micro-domain structure, which is considered to relate directly to the origin of the observed cluster glass behaviour in U(2)IrSi(3).