Size-controlled hydrothermal synthesis and electrochemical behavior of orthorhombic LiMnO2 nanorods

Large amount of uniform orthorhombic LiMnO₂ (o-LiMnO₂) nanorods was fabricated by a hydrothermal route in 180 °C using γ-MnOOH nanorods as precursors through an isomorphous ion exchange process. The size of as-obtained o-LiMnO₂ nanorods was determined by that of γ-MnOOH precursors, which could be deliberately controlled. The electrochemical performance of o-LiMnO₂ nanorods was characterized via galvanostatic tests, which suggested that the size of as-obtained products played an important role in their electrochemical performances.     

Hydrothermal synthesis of well-dispersed ultrafine N-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light

Ultrafine nitrogen-doped TiO₂ nanoparticles with narrow particle size distribution, good dispersion, and high surface area were synthesized in the presence of urea and PEG-4000 via a hydrothermal procedure. TEM observation, N₂ adsorption, XRD, UV-vis spectroscopy, the Raman spectroscopy and XPS analysis were conducted to characterize the synthesized TiO₂ particles. The synthesized TiO₂ particles were a mixture of 49.5% anatase and 50.5% rutile with a size of around 5 nm. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive Brilliant Blue KN-R under both UV and visible light. The synthesized TiO₂ particles showed much higher photocatalytic activity than a commercial P25 TiO₂ powder under both UV and visible light irradiations. The high performance is associated to N doping, the reduced particle size, good dispersion, high surface area, and a quantum size effect.     

Structure and photocatalytic properties of copper-doped rutile TiO2 prepared by a low-temperature process

Copper-doped titania with variable Cu/Ti ratios have been prepared via a simple aqueous-phase method at 85 °C. The obtained products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-vis absorption spectra analysis. The photocatalytic properties of the products were tested by photocatalytic degradation of aqueous brilliant red X-3B solution. The results showed that the sample with 2% copper doping has the best photocatalytic activity, which is 3 times that of undoped rutile titania. The effect of the doped copper on the structure and property of TiO₂ has also been discussed.     

Porous LiNi0.75Co0.25O2 microspheres prepared via a hydrothermal process as cathode material for lithium ion batteries

Porous LiNi_0.75Co_0.25O₂ microspheres are successfully prepared by a simple hydrothermal process by using H[Ni_0.75Co_0.25OOH]₃ and LiOH as starting materials in the presence of urea for the first time. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (S_BET), and electrochemical performance. The synthesized LiNi_0.75Co_0.25O₂ has a good electrochemical performance with an initial discharge capacity of 169.3 mA g⁻¹ and good capacity retention of 96.7% after 50 cycles at 0.2 C (25 mA g⁻¹). The electrochemical lithium ion insertion/extraction process is quite reversible even at 5 C. Furthermore, the structure in the charge-discharge process is stable and the impedance increased slowly during cycling.     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Effects of microwave drying on the microstructure and photocatalytic activity of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with highly photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate as precursor, and then dried in microwave oven. The prepared samples were characterized by XRD, SEM, TEM, HRTEM and N₂ adsorption-desorption measurement. The photocatalytic activity was evaluated by the photocatalytic degradation of acetone in air under UV light irradiation at room temperature. The effects of microwave drying on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. The results show that microwave drying not only promotes the growth of the pores but also greatly reduces the state of agglomeration within the powders. All the microwave-dried TiO₂ powders show higher photocatalytic activity than Degussa P-25 (P25) and the TiO₂ powders dried by conventional method.     

Improving the visible light photocatalytic activity of mesoporous TiO2 via the synergetic effects of B doping and Ag loading

B-doped together with Ag-loaded mesoporous TiO₂ (Ag/B–TiO₂) was prepared by a two-step hydrothermal method in the presence of boric acid, triblock copolymer surfactant, and silver nitrate, followed by heat treatment. The obtained samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption. It was revealed that all samples consist of highly crystalline anatase with mesoporous structure. For Ag/B–TiO₂, B was doped into TiO₂ matrix in the form of both interstitial B and substitutional B while Ag was deposited on the surface of B–TiO₂ in the form of metallic silver. Compared with the single B-doped or Ag-loaded TiO₂ one, mesoporous Ag/B–TiO₂ exhibits much higher visible light photocatalytic activity for the degradation of Rhodamine 6G, which can be ascribed to the synergistic effects of B doping and Ag loading by narrowing the band gap of the photocatalyst and preventing the fast recombination of the photogenerated charge carriers, respectively.     

Rapid microwave-assisted hydrothermal synthesis of Bi12TiO20 hierarchical architecture with enhanced visible-light photocatalytic activities

Flower-like Bi₁₂TiO₂₀ hierarchical nanostructures composed of numerous nanobelts were synthesized at 180 °C within 1 h by a microwave-assisted hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB) for the first time. The as-prepared products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) absorption spectroscopy. Furthermore, the hierarchical Bi₁₂TiO₂₀ nanostructures exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible-light irradiation than that of the samples prepared without CTAB. In addition, the role of CTAB cationic surfactant has been investigated thoroughly and a possible mechanism is proposed.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

Preparation of TiO2 hollow spheres for DSSC photoanodes

High crystallinity mesoporous TiO₂ hollow spheres (MHS-TiO₂) were prepared using the mesoporous carbon hollow sphere template. The MHS-TiO₂ contains mainly nanostructured anatase. The mesopore of the MHS-TiO₂ has a pore opening in the range of 400–600 nm. The refined extended X-ray absorption fine structure spectra indicate that the MHS-TiO₂ possesses less the 1st-shell Ti–O coordination numbers than the nano-TiO₂. More surface active species (A₂ ((Ti=O)O₄)) on the MHS-TiO₂ are also observed by the component fitted X-ray absorption near edge structure spectroscopy. The MHS-TiO₂ photoanode has a better DSSC conversion efficiency than the nano-TiO₂ one by at least 40%. Note that the N3 dye molecules are accessible to the mesopores of the MHS-TiO₂, and the loading time for N3 can be reduced by at least 70% if compared with those of the nano-TiO₂.     

Synthesis of nanocrystalline and mesoporous zinc sulphide from a single precursor Zn(SOCCH3)2Lut2 complex

We report the formation of mesoporous zinc sulphide, composed by the fine network of nanoparticles, which was formed via a single precursor Zn(SOCCH₃)₂Lut₂ complex. The complex was chemically synthesized using zinc carbonate basic, 3,5-lutidine and thioacetic acid, in air. The metal precursor complex was characterized using different conventional techniques. Thermogravimetric analysis (TGA) result indicates that the decomposition of the complex starts at 100 °C and continues up to 450 °C, finally yielding ZnS. ZnS nanocrystals were characterized by powder X-ray diffraction (XRD) technique, field emission scanning electron microscopy (FESEM), N₂-sorption isotherm, UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The grain diameter of nanocrystals was found to be 4-5 nm. The material followed Type-IV N₂-sorption isotherm, which is the characteristic of mesoporous materials. The band gap energy, as obtained from optical measurements was around 3.8 eV.     

Photocatalytic photodegradation of xanthate over C, N, S-tridoped TiO2 nanotubes under visible light irradiation

C, N, S-tridoped TiO₂ nanotubes were synthesized via hydrothermal synthesis and post-treatment, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), the Brunauer-Emmett-Teller method (BET), and UV-vis diffuse reflectance spectroscopy (DRS). The UV-diffuse reflectance spectra of all the C, N, S-tridoped TiO₂ nanotubes greatly extended the absorption edge to the visible light region, and the absorbance in the visible region increased with increasing molar ratio of thiourea to Ti (R), which could be attributed to C, N, S-tridoping in the form of cation C-doping, interstitial N-doping, cation S-doping, and adsorbed ions’ states. The photocatalytic activity of C, N, S-tridoped TiO₂ nanotubes was evaluated by photocatalytic photodegradation of potassium ethyl xanthate (KEX) under visible light irradiation. It was found that the photocatalytic activity of the prepared samples increased with increasing molar ratio of thiourea to Ti (R). At R=6, the photocatalytic activity of the tridoped sample TNTS-6 reached a maximum value. With further increase in R, photocatalytic activity of the sample decreased, which could be attributed to the high visible light activity resulting from the balance between visible light absorption and recombination of electron/hole pairs.     

Optical and photocatalytic properties of nanocrystalline TiO2 synthesised by solid-state chemical reaction

Nanoparticulate TiO₂ is of interest for a variety of technological applications, including optically transparent UV-filters and photocatalysts for the destruction of chemical waste. The successful use of nanoparticulate TiO₂ in such applications requires an understanding of how the synthesis conditions effect the optical and photocatalytic properties. In this study, we have investigated the effect of heat treatment temperature on the properties of nanoparticulate TiO₂ powders that were synthesised by solid-state chemical reaction of anhydrous TiOSO₄ with Na₂CO₃. It was found that the photocatalytic activity increased with the heat treatment temperature up to a maximum at 600 °C and thereafter declined. In contrast, the optical transparency decreased monotonically with the heat treatment temperature. These results indicate that solid-state chemical reaction can be used to prepare powders of nanoparticulate TiO₂ with properties that are optimised for use as either optically transparent UV-filters or photocatalysts.     

The synthesis and photoelectric study of 6,13-bis(4-propylphenyl)pentacene, and its TiO2 nano-sized composite films

The synthesized 6,13-bis(4-propylphenyl)pentacene(BPP) is much more soluble and stable than pentacene. The introduction of 4-propylphenyl group leads the solubility to 7.33 mg/mL in CHCl₃. In cyclic voltammetry (CV) test, it was found that its forbidden band gap is 1.88 eV. Moreover, a series of BPP-TiO₂ composites were constructed. Characterizations proved that an interaction between BPP and TiO₂ has probably occurred, leading to the generation of some novel properties. The most interesting result is that the forbidden band gaps of the composite materials are much smaller than that of BPP and TiO₂.     

Polyol-assisted synthesis of TiO2 nanoparticles in a semi-aqueous solvent

TiO₂ (anatase and rutile) nanoparticles with an average crystallite size of 20-40 nm have been prepared at room temperature by polyol-mediated synthesis technique in a semi-aqueous solvent medium using titanium iso-propoxide as the titanium source, acetone as the oil phase and ethylene glycol as the stabilizer. Phase and microstructure of the resultant materials have been characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photocatalytic degradation of acetaldehyde using TiO₂ nanoparticles was investigated by gas-chromatography technique.     

Theoretical design and experimental study of hydrothermal synthesis of KNbO3

In the framework of the Lencka-Riman thermodynamic model, we give a theoretical design for the hydrothermal synthesis of pure KNbO₃ powder in a K-Nb-O tri-component system, where the stability yield diagrams and the optimum conditions (i.e., synthesis temperature, precursor concentrations, solution pH) are provided. Additionally, a hydrothermal experiment is carried out to synthesize KNbO₃ powder by reacting niobium pentoxide with potassium hydroxide at a temperature above 523 K and highly alkaline conditions. It is found that the experiment is in great agreement with the theoretical design. This research shows that the newly developed Lencka-Riman model is a powerful theoretical tool for designing hydrothermal synthesis of new materials.     

Facile synthesis and electrochemical properties of hierarchical MnO2 submicrospheres and LiMn2O4 microspheres

Hierarchical MnO₂ submicrospheres have been successfully synthesized by a wet chemical method. The as-prepared products were characterized by means of XRD, SEM, FTIR, TG, and TEM. With the as-prepared MnO₂ submicrospheres as precursors, LiMn₂O₄ microspheres were conveniently prepared by a simple solid-state reaction between MnO₂ and LiOH at a temperature as low as 600 °C. Electrochemical properties of the as-prepared MnO₂ submicrospheres and LiMn₂O₄ microspheres as cathode materials in lithium ion cells were investigated by galvanostatic charge/discharge tests.     

Photophysical and enhanced daylight photocatalytic properties of N-doped TiO2/g-C3N4 composites

N-doped TiO₂/C₃N₄ composite samples were synthesized by heating the mixture of the hydrolysis product of TiCl₄ and C₃N₄ at different weight ratios. The samples were characterized by X-ray diffraction (XRD), Raman spectrum, UV–vis absorption spectrum, photoluminescence spectrum, X-ray photon electron spectrum (XPS) and surface photovoltage spectrum (SPS). The XRD and Raman results indicate that the introduction of C₃N₄ could inhibit the formation of rutile TiO₂. The composite samples show slight visible light absorption due to the introduction of C₃N₄. The XPS result reveals that some amount of nitrogen is doped into TiO₂, and C₃N₄ exists in the composite sample. The intensities of the SPS signal in the composite samples decrease with the rise in the amount of C₃N₄ in the samples. The photocatalytic activity was evaluated from the Rhodamine B (RhB) degradation under fluorescence light irradiation. The composite samples show significantly enhanced photocatalytic activities and the RhB self-sensitized photodegradation in this system was observed by measuring the photocurrent in the dye sensitized solar cell using the composite as the working electrode.     

Facile synthesis of monodispersed CeO2 nanostructures

CeO₂ nanostructures were successfully prepared by a facile and environmentally friendly mixed-solvothermal method under mild conditions. The X-ray diffraction (XRD) and transmission electron microscope (TEM) results indicated that the as-synthesized products were cubic CeO₂ polycrystalline structures with uniform diameters in the range of 10–20 nm and lengths up to 80 nm. X-ray photoelectron spectroscopy (XPS) spectra and EDX data demonstrated that stoichiometric CeO₂ was formed. A possible growth mechanism of the CeO₂ nanostructures was proposed. Moreover, ultraviolet absorption measurement revealed the band gap of the CeO₂ nanorods was estimated to be 3.85 eV, which is larger than the reported value for the bulk CeO₂ (E_g=3.2 eV). Enhancement of the band gap of the CeO₂ nanorods is attributed to the well-known quantum size effect.