Exchange of Thiol Ligands on CuInS2 Quantum Dots in High Boiling Solvents.

As-prepared quantum dots are covered with long-chain ligands to prevent aggregation. When quantum dots are used in optoelectronic devices such as solar cells and QD-LED, ligand exchange is necessary to replace long-chain ligands with short-chain ones to increase the efficiency of charge transfer from the quantum dots to the electrode. In this study, we successfully exchanged 1-dodecanethiol (DDT) ligands on CuInS2 quantum dots with mercaptopropionic acid (MPA) ligands by using a two-phase system of high-boiling hydrophilic and hydrophobic solvents. The ligand exchange to MPA was achieved by using diethylene glycol (DEG) or ethylene glycol (EG) as the hydrophilic phase and tetradecane as the hydrophobic phase. The ligand exchange rate increased with increasing ligand exchange temperature. When quantum dot sensitized solar cells (QDSSCs) were fabricated using the ligand-exchanged quantum dots, a positive correlation was observed between the progress of ligand exchange and short-circuit current density. This is because charge transfer efficiency from the quantum dots to the TiO2 electrode was improved by the ligand exchange. This work has shown that QDs synthesized using DDT can be applied to optoelectronic devices.

Preparation of Oriented ZnO Rod Arrays Using Hexagonal Plate-Like Particles as a Seed Layer.

ZnO rod film is a promising material for electrodes and sensors due to its large surface area and high electrical conductivity. One of the drawbacks of conventional ZnO rod film is the random orientation of rods. In this study, an oriented ZnO seed layer composed of hexagonal plate-like ZnO particles was prepared by dip-coating. An oriented ZnO rod film was then synthesized by growing this seed layer using a hydrothermal synthesis method. We optimized the concentration of the precursor and the hydrothermal treatment time to synthesize homogeneous ZnO rod arrays. The uniformity of the rod arrays was improved by applying a strong magnetic field (12 T) during hydrothermal treatment.

Spontaneously formed gradient chemical compositional structures of niobium doped titanium dioxide nanoparticles enhance ultraviolet- and visible-light photocatalytic performance.

Semiconductor photocatalysts showing excellent performance under irradiation of both ultraviolet (UV)- and visible (VIS)-light are highly demanded towards realization of sustainable energy systems. TiO2 is one of the most common photocatalysts and has been widely investigated as candidate showing UV/VIS responsive performance. In this study, we report synthesis of Nb doped TiO2 by environmentally benign mechanochemical reaction. Nb atoms were successfully incorporated into TiO2 lattice by applying mechanical energy. As synthesized Nb doped TiO2 were metastable phase and formed chemical compositional gradient structure of poorly Nb doped TiO2 core and highly Nb doped TiO2 surface after high temperature heat treatment. It was found that formed gradient chemical compositional heterojunctions effectively enhanced photocatalytic performance of Nb doped TiO2 under both of UV- and VIS-light irradiation, which is different trend compared with Nb doped TiO2 prepared through conventional methods. The approach shown here will be employed for versatile systems because of simple and environmentally benign process.

Interconnection of organic-inorganic hybrid nano-building blocks towards thermally robust mesoporous structures.

The use of organic-inorganic hybrid nanoparticles will enable a control of the characteristics of both the nanoparticles and constructed fine structures. In this study, we report the synthesis of acrylate-intercalated layered manganese, cobalt, and nickel hydroxide nanoparticles and their assembly into ordered mesoporous structures. Polymerization of the intercalated acrylates takes place by means of a radical initiator. The formed organic network improved the thermal stability of the layered hydroxides, which results in thermally robust mesoporous structures. Additionally, it is found that the polymerization can be initiated and progressed at 200 °C without any initiators for the layered nickel hydroxide system. This allows for the scalable solid-state thermal polymerization of intercalated acrylates and the formation of thermally robust hierarchically ordered meso/macroporous powders as well as mesoporous films. The electrochemical characterization reveals that the thermally robust mesoporous films having regulated mesopores allow for the effective diffusion of molecules/solvent compared with the films having collapsed mesoporous structures.

Size Effect of Hydroxide Nanobuilding Blocks and Nonionic Block Copolymer Templates on the Formation of Ordered Mesoporous Structures.

The use of precrystallized nanoparticles as nanobuilding blocks (NBBs) is a promising way to obtain mesoporous materials with crystalline walls. In this study, the size effects of both hydroxide NBBs and nonionic block copolymer (BCP) templates on the formation of ordered mesostructures are investigated. The diameter of layered nickel hydroxide NBBs was controlled at the sub-2 nm scale by an epoxide-mediated alkalinization process. Commercially available nonionic BCPs (gyration radii in the range of 11.9-43.9 Å) were used. Mesoperiodic structures were formed by the evaporation-induced self-assembly process. A proper size combination of hydroxide NBBs, smaller than 12.5 Å, and BCPs, larger than 19.9 Å, is shown to be necessary to form ordered mesostructures.

Organic-Inorganic Hybrid Nanocrystal-based Cryogels with Size-Controlled Mesopores and Macropores.

Nanocrystal-based processing has attracted significant interest for the fabrication of highly functional materials with controlled crystallinity and fine porous structures. In this study, we focused on the template-free synthesis of nanocrystal-based materials with size-tailored pores using layered nickel hydroxide intercalated with acrylate anions. Polymerization of the acrylates encouraged interconnection of the nanocrystals and the formation of homogeneous gel networks. Cryogels after freeze-drying had pores with an average diameter from 4.8 nm (mesoscale) to 68.9 nm (macroscale). It was found that the surface characteristics of starting nanocrystals determined the phase separation tendency of interconnected species from the reaction media and resultant porous structures. We believe that the present study can enable the design of template-free nanocrystal-based porous materials.

Enhanced visible-light photocatalytic activity of anatase-rutile mixed-phase nano-size powder given by high-temperature heat treatment.

Nano-size EVONIK AEROXIDE® P25 titanium dioxide, TiO2, powder was heat-treated at temperatures, 700-900°C, in air. An X-ray diffraction study showed that the P25 powder is composed of approximately 20 and approximately 80 mass% of rutile and anatase phases, respectively. It was also shown that the transformation from anatase to rutile induced by high-temperature heat treatment was almost completed at 750°C, whereas a small amount (less than 3 mass%) of anatase phase was still left even in the powder heat-treated at 900°C. The transformation behaviour was consistent with results obtained by Raman scattering spectroscopy. Raman experiments also indicated that high-temperature heating induced the formation of oxide ion vacancies. Powders were dispersed in methyl orange (MO) aqueous solution, and the bleach rate of MO was measured to evaluate photocatalytic activity under ultraviolet (UV)- and visible-light irradiation. After the heat treatment, the UV-light photocatalytic performance sharply deteriorated. Interestingly, visible-light photocatalytic activity was enhanced by high-temperature heating and reached the highest performance for an 800°C-heated sample, indicating that the P25 powder obtained high visible-light photocatalytic performance after heat treatment. Even after 900°C heat treatment, the photocatalytic performance was higher than that of as-received powder. Enhancement of photocatalytic activities was discussed in relation to visible light absorption and charge carrier transfer.

Tuning the size of aluminum oxide nanoparticles synthesized by laser ablation in water using physical and chemical approaches.

Colloidal solution of nano-sized spherical Al(2)O(3) particles were produced by nanosecond laser ablation upon irradiation on a corundum target in a distilled water environment. The effects of target inclination along the direction of laser irradiation and defocusing of the laser beam have been investigated in this study. The effect of the pH of the aqueous solution has also been studied. Synthesized particles were analyzed using transmission electron microscopy (TEM) to investigate particle shape and size distributions. Ablated nanoparticles (NPs) were spherical in shape, with the average particle size ranging from 8 to 18 nm in different operating conditions. Target inclination resulted in a decrease in the average particle size. Laser defocusing at the same power and thus with reduced fluence caused a decrease in the average size and standard deviation (SD), whereas defocusing that maintained the same fluence caused the reverse effect. Phase identification of NPs performed with high resolution TEM lattice images and fast Fourier transform indicated both a metastable γ-Al(2)O(3) phase and a stable α-Al(2)O(3) phase. X-ray diffraction analysis was also performed, which showed peaks of both α-Al(2)O(3) and γ-Al(2)O(3) with the presence of α- and γ-AlO(OH) polymorphs in acidic and alkaline solution, respectively. Surface conditions of the ablated particles representing the acidic and alkaline conditions were found to have a significant influence on both the size and crystallographic phase, which indicates it may be possible to induce size and phase transitions by changing the surface chemistry.

Potential use of only Yb2O3 in producing dense Si3N4 ceramics with high thermal conductivity by gas pressure sintering.

Yb2O3 is an efficient sintering additive for enhancing not only thermal conductivity but also the high-temperature mechanical properties of Si3N4 ceramics. Here we report the fabrication of dense Si3N4 ceramics with high thermal conductivity by the gas pressure sintering of α-Si3N4 powder compacts, using only Yb2O3 as an additive, at 1900 °C under a nitrogen pressure of 1 MPa. The effects of Yb2O3 content, sample packing condition and sintering time on the densification, microstructure and thermal conductivity were investigated. Curves of the density plotted against the Yb2O3 content exhibited a characteristic 'N' shape with a local minimum at 3 mol% Yb2O3 and nearly complete densification below and above this concentration. The effects of the sample packing condition on the densification, microstructure and thermal conductivity strongly depended on the Yb2O3 content. The embedded condition led to more complete densification but also to a decrease in thermal conductivity from 119 to 94 W m-1 K-1 upon 1 mol% Yb2O3 addition. The sample packing condition had little effect on the density and thermal conductivity (102-106 W m-1 K-1) at 7 mol% Yb2O3. The thermal conductivity value was strongly related to the microstructure.

Urea coordinated titanium trichloride Ti(III)[OC(NH)2]6Cl3: a single molecular precursor yielding highly visible light responsive TiO2 nanocrystallites.

A coordination complex, Ti(III)[OC(NH2)2]6Cl3, was first synthesized via reacting hot alcoholic solutions of TiCl3 and urea, which was subsequently employed as a molecular precursor for nanocrystalline TiO2 via thermal decomposition. Fourier transform IR spectroscopy confirmed C=O-->Ti coordination bond formation, while Rietveld refinement revealed a hexagonal crystal structure (space group: Pc1) for the complex with a = b = 16.438(4) A, c = 15.423(3) A, alpha = beta = 90 degrees , gamma = 120 degrees , and V = 3608.9(13) A3. Thermal decomposition and phase evolution processes of the complex were investigated in air by combined means of elemental analysis, Fourier transform IR, differential thermal analysis/thermogravimetry, X-ray diffraction, and Raman spectroscopy. Characterizations of the resultant TiO2 powders were achieved by scanning electron microscopy, high-resolution transmission electron microscopy, the Brunauer-Emmett-Teller analysis, thermal desorption spectroscopy, and UV-vis spectroscopy. Simultaneous doping of C, N, and Cl was realized upon pyrolyzing the molecular precursor in air, leading to significantly lowered direct and indirect interband transition energies of the resultant TiO2. As a consequence, the anatase nanopowders obtained at 450 and 500 degrees C, with specific surface areas of 97.8 and 64.1 m2/g, respectively, exhibit significantly higher efficiency than Degussa P25 in the bleaching of methyl orange solution under visible light (mainly consisting two wavelengths of 405 and 436 nm at 81:100 intensity ratio) irradiation, either at a fixed weight of TiO2 loading or at a fixed surface area of the loaded TiO2 powder.

Phase structure and luminescence properties of Eu3+-doped TiO2 nanocrystals synthesized by Ar/O2 radio frequency thermal plasma oxidation of liquid precursor mists.

Eu3+-doped TiO2 luminescent nanocrystals have been synthesized in this work via Ar/O2 thermal plasma oxidizing mists of liquid precursors containing titanium tetra-n-butoxide and europium(III) nitrate, with varied O2 input in the plasma sheath (10-90 L/min) and Eu3+ addition in the precursor solution (Eu/(Ti + Eu) = 0-5 atom%). The resultant nanopowders are mixtures of the anatase (30-36 nm) and rutile (64-83 nm) polymorphs in the studied range, but the rutile fraction increases steadily at a higher Eu3+ addition, as revealed by X-ray diffraction (XRD) and Raman spectroscopy, because of the creation of oxygen vacancies in the TiO2 gas clusters by substitutional Eu3+ doping. The amount of Eu3+ that can be doped into a TiO2 lattice was limited up to 0.5 atom%, above which Eu2Ti2O7 pyrochlore was formed in the final products. High resolution transmission electron microscopy (HRTEM) observation indicates that the particles are dense and have sizes ranging from several nanometers up to 180 nm. Efficient nonradiative energy transfer from the TiO2 host to Eu3+ ions, which was seldom reported in the wet-chemically derived nanoparticles or thin films of the current system, was confirmed by combined studies of excitation, UV-vis (ultraviolet-visible), and PL (photoluminescence) spectroscopy. As a consequence of this, bright red emissions were observed from the plasma-generated nanopowders either by exciting the TiO2 host with UV light shorter than 405 nm or by directly exciting Eu3+ at a wavelength beyond the absorption edge (405 nm) of TiO2.