The size-dependent valence and conduction band-edge energies of Cu quantum dots.

Ultra-small metal particles having band gaps are regarded as a new class of functional materials. We investigated the size dependencies of the band-edge energies on Cu quantum-dots in the size range of 0.7-2.1 nm. The extremely high conduction band-edge energies owing to the strong quantum-size effects were observed for sizes below 1 nm.

Removal of hexavalent chromium from water by Z-scheme photocatalysis using TiO2 (rutile) nanorods loaded with Au core-Cu2O shell particles.

All-solid-state Z-scheme photocatalysts, containing Cu2O, TiO2 (rutile), and Au as the electron mediator, were prepared and applied to the reduction of Cr(VI) in aqueous solutions. The Cu2O-Au-TiO2 composites were prepared by loading Au core-Cu2O shell hemisphere particles on TiO2 (rutile) nanorods using a two-step photocatalytic deposition process. Under ultraviolet-visible (UV-vis) light illumination, the Cu2O-Au-TiO2 composites exhibited higher photocatalytic Cr(VI) reduction activities than those exhibited by single TiO2 (rutile) and Cu2O. In this reaction, a precipitate containing Cr, which was considered to be Cr(OH)3, was deposited site-selectively on the Au core-Cu2O shell particles of the composites, indicating that the reduction site of the composite was Cu2O, and the reaction proceeded according to the Z-scheme. The Cu2O-Au-TiO2 composites also exhibited photocatalytic activity under visible light illumination. The oxidation state of Cu in the Cu2O-Au-TiO2 composite gradually changed from Cu(I) to Cu(II) during the photocatalytic Cr(VI) reduction. However the composite maintained its high photocatalytic performance even after oxidation. The role of Au in the Cu2O-Au-TiO2 composite was examined by comparing the properties of the Cu2O-Au-TiO2 composite with those of the Cu2O-TiO2 composite prepared via direct Cu2O deposition on TiO2.

Hydrothermal Synthesis and Crystal Structure of a Mixed-Valence Bismuthate, Na3Bi3O8.

Four types of bismuth oxides, Na3Bi3O8, NaBiO3, α-Bi2O3, and ε-Bi2O3, were obtained by hydrothermal reactions using NaBiO3·nH2O in NaOH solution. The crystal structure of a new phase (Na3 Bi3+)Bi25+O8 ((Na0.75Bi0.25)2BiO4) was determined by using single crystal X-ray diffraction data, and this compound was found to show a Na2MnCl4-related structure with a monoclinic system (space group, Pm) with the following lattice parameters: a = 5.990 (2) Å, b = 3.335 (2) Å, c = 10.108 (2) Å, and ß = 91.08 (3)°. The final R-factors R1 and wR2 were 0.041 and 0.090 (all data), respectively. The new phase was composed of mixed valence states of Bi (Bi3+ and Bi5+, with a mean Bi valence of 4.30) with five distinct Bi sites, where two Bi5+ (Bi1 and Bi2) fully occupied the distorted octahedral sites and three Bi3+ (Bi3, Bi4, and Bi5) were statistically distributed at the split sites with Na+ (Na3, Na4, and Na5). The Na6 site is fully occupied. The distorted Bi5+O6 octahedra formed one-dimensional chains via edge-sharing along the b-axis, with the chains held by Bi3+/Na+ split sites. The structural feature except for the split distribution of Bi3+/Na+ was classified as a Na2MnCl4-type structure. DFT calculations based on a model discounting the split distribution of Bi3+/Na+ indicated that Bi 6s and O 2p orbitals form sp hybridization at the conduction band. This new mixed valence bismuth oxide exhibited photocatalytic activity for phenol degradation under visible light irradiation. In addition to Na3Bi3O8, the hydrothermal reaction using NaBiO3·nH2O in NaOH solution yielded micrometer-sized single crystals of an ilmenite-type NaBiO3 and two polymorphs of bismuth oxides with monoclinic (α-Bi2O3) and orthorhombic (ε-Bi2O3) structures, depending on the reaction temperature and NaOH concentration.

Hydrothermal Synthesis and Crystal Structure of a (Ba0.54K0.46)4Bi4O12 Double-Perovskite Superconductor with Onset of the Transition Tc ∼ 30 K.

A new superconducting double perovskite was successfully synthesized by a low-temperature hydrothermal reaction at 240 °C. The crystal structure refinement of this double perovskite was done by single-crystal X-ray diffraction, and it had a cubic unit cell of a = 8.5207(2) Å with space group Im3̅m (No. 229). This superconducting double-perovskite chemical composition was estimated by electron probe microanalysis and was similar to the refined data. The superconducting transition temperature of the double perovskite was ∼30 K; the electrical resistivity began to fall at ∼25 K, and zero resistivity occurred below 7 K. Moreover, temperature-dependent resistivity under various magnetic fields and isothermal magnetization measurements ensured the nature of a type II superconductor for the sample. Finally, the metallic nature of the material was investigated by a first-principles study.

Enhanced Supercapacitor Performance Based on CoAl Layered Double Hydroxide-Polyaniline Hybrid Electrodes Manufactured Using Hydrothermal-Electrodeposition Technology.

Electrodes with nanosheet architectures can offer the possibility to achieve enhanced energy storage performance. Herein, we have designed and synthesized novel nanosheet structures of CoAl layered double hydroxide (LDH)-polyaniline (PANI) nanocomposite thin films by a hydrothermal-electrodeposition method. The molecular structure, crystal structure, morphology and chemical composition of the composites were characterized by FT-IR, XRD (SXRD), FESEM, and XPS, whereas their electrochemical properties were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge tests. Compared with the unmodified CoAl LDH, the CoAl LDH-PANI exhibits significantly improved the specific capacitance and cyclic stability. The composite exhibits a high specific capacitance of 528 F/g at a current density of 10 A/g and excellent cyclic stability with an increase of the specific capacitance of 42.7% after 6000 cycle tests. We revealed the degradation behavior of PANI in 1 M KOH/KCl electrolyte, and the active degradation products also further increased the total specific capacitance of the composite. The enhanced electrochemical performance of the nanocomposite can be attributed to its well-designed nanostructure and the synergistic effects of each component. By analyzing the band structure and density of states of CoAl LDH and PANI, we proposed the possible mechanism of synergistic effect in a new perspective.

Hydrothermal Synthesis of Pyrochlore-Type Pentavalent Bismuthates Ca2Bi2O7 and Sr2Bi2O7.

The pyrochlore-type Ca2Bi2O7 and Sr2Bi2O7 have been synthesized from a low-temperature hydrothermal route using NaBiO3·nH2O as a starting material. The crystal structures of these compounds were refined using synchrotron powder X-ray diffraction data. The cell parameters were found to be a = 10.75021 (5) Å and 10.94132 (6) Å for Ca2Bi2O7 and Sr2Bi2O7, respectively. Density functional theory calculations showed the metallic band structure, but the negligible mixing of O2 2p bands with the A-site alkaline-earth-metal states and weak overlap with the conduction bands result in the semiconducting behavior.

Circumstances of La, Eu, Dy, and Yb Cations Intercalated via Ion Exchange in γ-Zirconium Phosphate.

Both α- and γ-zirconium phosphate were examined for use as ion exchangers for recovery of rare earth elements. Trivalent rare earth elements can be partially substituted for protons in the interlayer space, and γ-zirconium phosphate shows a much better ion exchange competency than α-zirconium phosphate. The exchanged cation of the rare earth elements might be related to different amounts of oxygen from P-OH and H2O, and these rare earth elements were thus positioned at a different separations from the zirconium phosphate layer. The radial structure function (RSF) curve from extended X-ray absorption fine structure data implied that the calibrated M-O distance and coordination number changed with the ionic radius. The calibrated M-O distances from RSF were 2.52, 2.42, 2.38, and 2.28 for La, Eu, Dy, and Yb, respectively. The coordination numbers of oxygen for Yb were approximately 7 and greater than 10 for La and Eu, respectively. These smaller coordination numbers for smaller cations may result from the strong interaction between the cations and the zirconium phosphate layer. The Debye-Waller factor also increased with an increase in the ionic radius. These factors show a strong relation to the coordination state of rare earth elements in the unit cell of the γ-zirconium phosphate and to the interaction strength.

Crystal Structure, Thermal Behavior, and Photocatalytic Activity of NaBiO3· nH2O.

The crystal structure of NaBiO3· nH2O was refined using synchrotron powder X-ray diffraction and was assigned to a trigonal unit cell (space group P3̅) consisting of layered structures formed by edge-sharing BiO6 octahedra and consisting of an interlayer composed of water molecules sandwiched between two layers of sodium atoms, perpendicular to the c axis. An intermediate phase was observed during the dehydration of the hydrated compound. Density of state calculations showed hybridization of the Bi 6s and O 2p orbitals at the bottom of the conduction bands for both the hydrated and the dehydrated phases, which narrows the band gap and promotes their photocatalytic activity in the visible region.

Formation of Uniform and High-Coverage Monolayer Colloidal Films of Midnanometer-Sized Gold Particles over the Entire Surfaces of 1.5-in. Substrates.

We report a simple and facile method for fabricating monolayer colloidal films of alkanethiol-capped gold nanoparticles (AuNPs) on glass substrates. The new method consists of two sequential sonication processes. The first sonication is performed to obtain a well-dispersed state of alkanethiol-capped AuNPs in hexane/acetone in the presence of a substrate. After additional static immersion in the colloidal solution for 5 min, the substrate is subjected to sonication in hexane. By using this method, we succeeded in forming uniform and stable assemblies of midnanometer-sized AuNPs (14, 34, and 67 nm in diameter) over the entire surface of 10-mm square glass substrates in a short processing time of less than 10 min. It was also demonstrated that this method can be applied to a 1.5-in. octagonal glass substrate. The mechanism of monolayer colloidal film formation was discussed based on scanning electron microscopy observations at each preparation step. We found that the second sonication was the key process for uniform and high-surface-coverage colloidal film formation of midnanometer-sized AuNPs. The second sonication promotes the migration of AuNPs on top of the monolayer in contact with the substrate surface, decreasing both the multilayer region and the bare surface area. Eventually, a nearly perfect monolayer colloidal film is formed.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin ß increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Assembly of Mid-Nanometer-Sized Gold Particles Capped with Mixed Alkanethiolate SAMs into High-Coverage Colloidal Films.

We investigated the influence of the mixed n-alkanethiolate self-assembled monolayer (SAM) formed on gold nanoparticles (AuNPs: 50.0 ± 3.2 nm in diameter) on their assembly into colloidal films. Dodecanethiol and octadecanethiol were selected as the short- and long-chain alkanethiols, respectively. The mixed SAMs were formed by immersing AuNPs in a mixed alkanethiol solution at different molar ratios. Au colloidal films were fabricated on indium tin oxide substrates by our previously reported hybrid method. The composition of the two alkanethiolates in the SAM was deduced from the intensity ratio of two Raman bands at 1080 and 1105 cm(-1). The surface coverage of the colloidal films increased by forming equimolar or dodecanethiolate-dominant mixed SAMs on AuNPs instead of a pure dodecanethiolate or octadecanethiolate SAM. The highest coverage exceeded 80%. This improvement is attributed to the high dispersion stability of AuNPs covered with equimolar or dodecanethiolate-dominant mixed SAMs.

Preparation of a titania/X-zeolite/porous glass composite photocatalyst using hydrothermal and drop coating processes.

Combinations of TiO2 photocatalysts and various adsorbents have been widely studied for the adsorption and photocatalytic decomposition of gaseous pollutants such as volatile organic compounds (VOCs). Herein, a TiO2-zeolite-porous glass composite was prepared using melt-quenching and partial sintering, hydrothermal treatment, and drop coating for preparation of the porous glass support and X-zeolite and their combination with TiO2, respectively. The obtained composite comprised anatase phase TiO2, X-zeolite, and the porous glass support, which were combined at the micro to nanometer scales. The composite had a relatively high specific surface area of approximately 25 m2/g and exhibited a good adsorption capacity for 2-propanol. These data indicated that utilization of this particular phase-separated glass as the support was appropriate for the formation of the bulk photocatalyst-adsorbent composite. Importantly, the photocatalytic decomposition of adsorbed 2-propanol proceeded under UV light irradiation. The 2-propanol was oxidized to acetone and then trapped by the X-zeolite rather than being released to the atmosphere. Consequently, it was demonstrated that the micrometer-scaled combination of TiO2 and zeolite in the bulk form is very useful for achieving both the removal of gaseous organic pollutants and decreasing the emission of harmful intermediates.

Particle size dependence of the surface-enhanced Raman scattering properties of densely arranged two-dimensional assemblies of Au(core)-Ag(shell) nanospheres.

We investigated the dependence of the surface-enhanced Raman scattering (SERS) activity of densely arranged two-dimensional assemblies of spherical Au(core)-Ag(shell) nanoparticles (Au/AgNSs) on the nanoparticle diameter. The size-controlled Au/AgNSs were synthesized using the Au nanosphere seed-mediated growth method without any bulky stabilizers. The diameters of the Au/AgNSs were 38, 53, and 90 nm and the ratio of the total diameter to the Au core diameter was adjusted to ca. 2.0. Extinction spectra of the colloidal solutions of these nanoparticles exhibited the prominent peak of the localized surface plasmon resonance (LSPR) of Ag and therefore the Au/AgNSs exhibited LSPR properties almost the same as Ag nanospheres. It was confirmed from SEM observation that the organic solvent-mediated liquid-liquid interface assembly technique easily generated densely arranged two-dimensional assemblies of the nanospheres. The extinction spectra of all the assemblies exhibited a prominent broad peak ranging from 500 nm to the near-infrared region, which is assigned to the longitudinal LSPR mode of the coupling nanospheres. The extinction intensity increased with increasing nanosphere diameter. The SERS activities of these assemblies were investigated using p-aminothiophenol as a probe molecule. The result revealed that the enhancement factor (EF) of the Raman signal dramatically increased upon increasing the particle diameter. The maximum EF obtained with a laser excitation wavelength of 785 nm was 1.90 × 10(6) for a nanosphere diameter of 90 nm. This renders the two-dimensional assemblies of the plasmonic Au/AgNSs promising for the development of highly sensitive SERS sensor platforms due to their strong electromagnetic effect.

Refractive index susceptibility of the plasmonic palladium nanoparticle: potential as the third plasmonic sensing material.

We demonstrate that Pd nanospheres exhibit much higher susceptibility of the localized surface plasmon resonance (LSPR) peak to medium refractive index changes than commonly used plasmonic sensing materials such as Au and Ag. The susceptibility of spherical Au nanoparticle-core/Pd-shell nanospheres (Au/PdNSs, ca. 73 nm in diameter) was found to be 4.9 and 2.5 times higher, respectively, than those of Au (AuNSs) and Ag nanospheres (AgNSs) having similar diameters. The experimental finding was theoretically substantiated using the Mie exact solution. We also showed from a quasi-static (QS) approximation framework that the high susceptibility of Pd LSPR originates from the smaller dispersion of the real part of its dielectric function than those of Au and Ag LSPR around the resonant wavelength. We conclude that the Pd nanoparticle is a promising candidate of "the third plasmonic sensing material" following Au and Ag to be used in ultrahigh-sensitive LSPR sensors.

Fabrication of dense two-dimensional assemblies over vast areas comprising gold(core)-silver(shell) nanoparticles and their surface-enhanced Raman scattering properties.

Fabrication of dense two-dimensional assemblies consisting of gold(core)-silver(shell) nanoparticles and the resulting peculiar surface-enhanced Raman scattering (SERS) activity are reported. The assemblies were prepared via assembly at air-toluene interfaces by drop-casting toluene solutions containing the nanoparticles protected with octadecylamine molecules onto glass plates. This simple process, which does not require special apparatus or significant fabrication time, leads to uniform assemblies over vast areas (~34 cm(2)). In the SERS measurements, the high spatial reproducibility of the SERS signals from p-aminothiophenol adsorbed on the assemblies over vast areas demonstrates that this method is useful for the quantitative investigation of SERS mechanisms. Under 532 nm laser excitation, the difference in the enhancement factors of the SERS signals at the a1 mode between assemblies consisting of gold, silver, and core-shell nanoparticles can be explained by the degree of overlap of the excitation wavelength with their plasmon coupling modes. In contrast, under 785 nm excitation, even though the plasmon band of the core-shell nanoparticle assemblies does not significantly overlap with the excitation wavelength as compared with that of gold nanoparticle assemblies, the enhancement factor from the core-shell nanoparticle assemblies was stronger than those from the gold nanoparticle assemblies. Therefore, we have demonstrated that the gold(core)-silver(shell) nanoparticle assemblies are excellent SERS active materials, which have strong electromagnetic mechanism (EM) as well as chemical mechanism (CM) effects due to the silver shells.

Various factors affecting photodecomposition of methylene blue by iron-oxides in an oxalate solution.

The effect of various factors on the photodecomposition of methylene blue (MB) by iron oxides calcined at various temperatures in various concentrations of oxalate solutions was investigated by illuminating with UV, visible and solar radiation. Iron oxides were prepared by a gel evaporation method and calcined at 200-700 degrees C. XRD showed that the as-synthesized iron oxides were amorphous, but formed maghemite (gamma-Fe(2)O(3)) at 200-400 degrees C and hematite (alpha-Fe(2)O(3)) at > or =500 degrees C. The effect of the various iron oxides, their contents, the oxalate concentration and wavelength of the light source (UV, visible and solar) were all found to strongly influence MB photodecomposition. The optimal contents of the iron oxides increased greatly from 25 to 2000 mg/L at higher calcining temperatures. The MB photodecomposition rate at each optimal iron oxide content was related to the calcining temperature in the order 700 degrees C6, consistent with the presence of iron-oxalate complexes. A much higher concentration of hydroxyl radicals was generated in the present system compared with those from a commercial TiO(2) (ST-01), as determined by the coumarin method. Since this process does not require the addition of hydrogen peroxide and shows good efficiency even under solar light, it is an economically viable method for pre-treating and/or decolorizing wastewaters containing dyes.