Evolution of zirconia coating layer on rutile TiO2 surface and the pigmentary property

Zirconia-coated rutile TiO₂ composites were prepared by the chemical liquid deposition method starting from rutile TiO₂ and ZrOCl₂. The amorphous zirconia coating layers were anchored at the TiO₂ surface via Zr-O-Ti bond. The formation of continuous and dense zirconia coating layers was dependent on the pH value of the reaction solution and the mole ratio of ZrOCl₂ to TiO₂. As compared to the naked rutile TiO₂, the water dispersibility, whiteness, brightness, and relative light scattering index of the zirconia-coated rutile TiO₂ composites were increased.     

Evolution of structural and optical properties of rutile TiO2 thin films synthesized at room temperature by chemical bath deposition method

Nanocrystalline thin films of TiO₂ were prepared on glass substrates from an aqueous solution of TiCl₃ and NH₄OH at room temperature using the simple and cost-effective chemical bath deposition (CBD) method. The influence of deposition time on structural, morphological and optical properties was systematically investigated. TiO₂ transition from a mixed anatase–rutile phase to a pure rutile phase was revealed by low-angle XRD and Raman spectroscopy. Rutile phase formation was confirmed by FTIR spectroscopy. Scanning electron micrographs revealed that the multigrain structure of as-deposited TiO₂ thin films was completely converted into semi-spherical nanoparticles. Optical studies showed that rutile thin films had a high absorption coefficient and a direct bandgap. The optical bandgap decreased slightly (3.29–3.07 eV) with increasing deposition time. The ease of deposition of rutile thin films at low temperature is useful for the fabrication of extremely thin absorber (ETA) solar cells, dye-sensitized solar cells, and gas sensors.     

Tailoring optical properties of TiO2 nanowires coated with Ag nanoparticles by plasmon coupling of Ag nanoparticles

TiO₂ nanowires were grown on titanium foil by an alkali hydrothermal growth method. The as-synthesized nanowires are structurally uniform with diameters of 50-100 nm and lengths of up to a few micrometers. The as-prepared TiO₂ nanowires were coated with Ag nanoparticles by reducing AgNO₃ in solution. The experimental results indicate that the Ag nanoparticles can aggregate together on the surfaces of TiO₂ nanowires by interconnection between nanoparticles. The degree of aggregation of Ag nanostructures can be controlled by changing the concentrations of Ag nanoparticles. The as-prepared nanostructures exhibit a wide optical absorption from 387 to 580 nm that can be easily tuned by controlling the degree of aggregation of Ag nanostructures. The results reveal that optical properties of the Ag-coated TiO₂ nanowires can be enhanced by plasmon coupling of Ag nanoparticles. The as-prepared nanostructures may find potential applications in the field of solar cells.     

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.     

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.     

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.     

Electrochemical properties of carbon-coated LiFePO4 synthesized by a modified mechanical activation process

Carbon-coated lithium iron phosphate (LiFePO₄/C) composites were synthesized by conventional mechanical activation (MA) process and also by a modified MA process. Phase-pure particles were obtained of ∼100 nm size with a nano-meter thick web of carbon surrounding the particles. The composite prepared by the modified MA process shows good performance as cathode material in lithium cells at room temperature. A high performance was achieved at 0.1 C-rate with >96% utilization of the active material. A stable cycle performance even at higher C-rates was achieved with a cathode that has a total carbon content of only 12 wt%. The use of the modified MA process to synthesize LiFePO₄/C has promise to be an efficient process to decrease the total carbon content of the cathode, resulting in the enhanced energy density.     

Ag/TiO2 sol prepared by a sol–gel method and its photocatalytic activity

Ag/TiO₂ sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. TiCl₄ was converted to Ti(OH)₄ gel. The Ag/TiO₂ sol was prepared by a process where H₂O₂ was added and then heated at 90–97 °C. After condensation reaction and crystallization, a transparent sol with suspended Ag/TiO₂ was formed. Ag/TiO₂ was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, contact angle analysis, and X-ray photoelectron spectroscopy. The photocatalytic properties of Ag/TiO₂ film were evaluated by degradation of methylene blue in aqueous solution under UV light irradiation. The suspended Ag/TiO₂ particles were rhombus primary particles with the major axis ca. 40 nm and the minor axis ca. 10 nm. Ag nanoparticles were well dispersed on TiO₂ and the particle size was only 1–2 nm. Ag could restrain the recombination of photo-generated electrons and holes effectively. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The thin film had strong hydrophilicity after being illuminated by UV light. Ag/TiO₂ film showed a significant increase in photocatalytic activity compared to the TiO₂ film. The high amount of surface hydroxyls on Ag/TiO₂ film also played an important role in its photocatalytic activity.     

Synthesis,photophysical properties,and photocatalytic applications of Bi doped NaTaO3 and Bi doped Na2Ta2O6 nanoparticles

Phase formation and photophysical properties of bismuth doped sodium tantalum oxide (perovskite, defect pyrochlore) nanoparticles prepared by a hydrothermal method were studied in detail. It was revealed that the synthesis conditions like NaOH concentration and bismuth precursor (NaBiO₃·2H₂O) markedly affect the crystal structure of sodium tantalum oxide. At low NaOH concentration and high bismuth precursor (NaBiO₃·2H₂O) content, Bi doped Na₂Ta₂O₆ (defect pyrochlore) phase was predominantly formed, while at higher NaOH concentration, Bi doped NaTaO₃ (perovskite) phase was formed. It was observed that the defect pyrochlore (Bi doped Na₂Ta₂O₆) phase was formed and stabilized by the presence of dopant precursor (NaBiO₃·2H₂O). The chemical analysis of the samples confirmed the doping of Bi³⁺ cations in both phases. Doping of bismuth enabled visible light absorption up to 500 nm in perovskite and defect pyrochlore type sodium tantalum oxide. Bi doped NaTaO₃ samples showed better performance for the photocatalytic degradation of rhodamine B than that of Bi doped Na₂Ta₂O₆, under visible light irritation (λ>420 nm). The present results shed light on phase formation of sodium tantalate and these results are useful in understanding properties of NaTaO₃ based compounds, synthesized by the hydrothermal method.     

Low-temperature hydrothermal synthesis of highly photoactive mesoporous spherical TiO2 nanocrystalline

TiO₂ microspheres with mesoporous textural microstructures and high photocatalytic activity were prepared by hydrothermal treatment of mixed solution of titanium sulfate and urea with designed time. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption measurements. The photocatalytic activity was evaluated via the photocatalytic oxidation of acetone in air at room temperature. The results show that the hydrothermal time significantly influences on the morphology, microstructure and photocatalytic activity of the as-prepared samples. With increasing hydrothermal time, specific surface areas and pore volumes decrease, contrarily, the crystallite size and relative anatase crystallinity increase. The photocatalytic efficiency of the as-prepared samples is obviously higher than that of commercial Degussa P25 (P25) powders. Especially, the as-prepared TiO₂ powders by hydrothermal treatment for 7 h shows the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2 times.     

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.     

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.     

Synthesis and enhanced photocatalytic activity of NaNbO3 prepared by hydrothermal and polymerized complex methods

We prepared NaNbO₃ by several methods, namely solid-state reaction (SSR), hydrothermal (HT) and polymerized complex (PC) methods, and investigated the relationships between the photocatalytic activity and the particle size and morphology. The photocatalytic activity was evaluated by H₂ evolution from an aqueous methanol solution and pure water splitting in the presence of the Pt(0.5 wt%)/NaNbO₃ and RuO₂(1.25 wt%)/NaNbO₃, respectively. It is found that the sample prepared by PC with smallest particles exhibits the highest photocatalytic activity in both reactions. Moreover, the HT sample with the cubic and rectangular shape also shows the enhanced photocatalytic activity for H₂ evolution from an aqueous methanol solution in comparison with that of the sample prepared by SSR.     

Synergistic effect of efficient adsorption g-C3N4/ZnO composite for photocatalytic property

Novel g-C₃N₄/ZnO composite photocatalyst was synthesized from an oxygen-containing precursor by direct thermal decomposition urea in air without any other templates assistance. Different percentages of g-C₃N₄ were hybridized with ZnO via the monolayer-dispersed method. The prepared g-C₃N₄/ZnO composites were characterized by XRD, SEM, UV–vis diffuse reflectance spectra (DRS), FT-IR, TEM and XPS. The composites showed much higher efficiency for degradation of Rhodamine B (RhB) than ZnO under UV and visible light irradiation. Especially, the photocatalytic efficiency was the highest under UV light irradiation when the percentage of g-C₃N₄ was 6%. The improved photocatalytic activity may be due to synergistic effect of photon acquisition and direct contact between organic dyestuff and photocatalyst. Then, effective separation of photogenerated electron–hole pairs at the interface of g-C₃N₄ is an important factor for improvement of photocatalytic activity. This work indicates that g-C₃N₄ hybrid semiconductors photocatalyst is a promising material in pollutants degradation.     

Stable cycle-life properties of Ti-doped LiFePO4 compounds synthesized by co-precipitation and normal temperature reduction method

Submicron-sized LiFePO₄ and Ti-doped LiFePO₄ cathode materials were synthesized by a reformative co-precipitation and normal temperature reduction method, for which Ti ions were added in the process of preparing precursors to pursue a kind of sufficient and homogenous doping way. ICP and XRD analyses indicate that Ti ions were sufficiently doped in LiFePO₄ and did not alter its crystal structure. It is noted that higher Ti ions doping levels are conducive to electrochemical performance of LiFePO₄, especially on the aspect of stable cycle-life at higher C rates. The sample doped with 3 at% Ti shows the most impressive cycling performance, even after 100 cycles, discharge capacity of 133 mAh g⁻¹ was obtained (102.3% of its initial value) at 1C rate, and the discharge decreased little from 124 to 120 mAh g⁻¹ (96.8% of its initial value) at 2C rate.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

Preparation, characterization and photocatalytic activity of metal-loaded NaNbO3

Fe-, Ni-, Co- and Ag- loaded NaNbO₃ catalysts were prepared and their activities have been investigated in the reaction of photocatalytic hydrogen generation. Me/NaNbO₃ were synthesized by impregnation of NaNbO₃ in an aqueous solution of metal nitrates and then by calcination at the temperature of 400 °C. The crystallographic phases and optical and vibronic properties were examined by X-ray diffraction (XRD) and diffuse reflectance (DR) UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM) and an energy dispersive X-Ray spectrometer (EDX) as its mode. The detailed analysis has revealed that all the investigated catalysts exhibit high crystallinity and the presence of Fe₂O₃, NiO, Co₃O₄ and Ag₂O oxides on Me/NaNbO₃ was confirmed. Finally, the influence of different metal loadings (Fe, Ni, Co and Ag) on the photocatalytic activity of NaNbO₃ for photocatalytic hydrogen generation has been investigated. Here we report that among all the Me/NaNbO₃ photocatalysts Ag-loaded NaNbO₃ exhibited higher photocatalytic efficiency for photocatalytic hydrogen generation than NaNbO₃.     

Magnetic properties of prussian blue modified Fe3O4 nanocubes

Size controlled cubic Fe₃O₄ nanoparticles in the size range 90–10 nm were synthesized by varying the ferric ion concentration using the oxidation method. A bimodal size distribution was found without ferric ion concentration and the monodispersity increased with higher concentration. The saturation magnetization decreased from 90 to 62 emu/g when the particle size is reduced to 10 nm. The Fe₃O₄ nanoparticles with average particle sizes 10 and 90 nm were surface modified with prussian blue. The attachment of prussian blue with Fe₃O₄ was found to depend on the concentration of HCl and the particle size. The saturation magnetization of prussian blue modified Fe₃O₄ varied from 10 to 80 emu/g depending on the particle size. The increased tendency for the attachment of prussian blue with smaller particle size was explained based on the surface charge. The prussian blue modified magnetite nanoparticles could be used as a radiotoxin remover in detoxification applications.     

Nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A method of preparing the nanoparticles of CaCu₃Ti₄O₁₂ (CCTO) with the crystallite size varying from 30 to 200 nm is optimized at a temperature as low as 680 °C from the exothermic thermal decomposition of an oxalate precursor, CaCu₃(TiO)₄(C₂O₄)₈·9H₂O. The phase singularity of the complex oxalate precursor is confirmed by the wet chemical analyses, X-ray diffraction, FT-IR and TGA/DTA analyses. The UV-vis reflectance and ESR spectra of CCTO powders indicate that the Cu(II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square-planar geometry with increasing annealing temperature. The HRTEM images have revealed that the evolution of the microstructure in nanoscale is related to the change in Cu(II) coordination around the surface regions for the chemically prepared powder specimens. The nearly flattened tetrahedral geometry prevails for CuO₄ in the near surface regions of the particles, whereas square-planar CuO₄ groups are dominant in the interior regions of the nanoparticles. The powders derived from the oxalate precursor have excellent sinterability, resulting in high-density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25 °C, accompanied by low dielectric loss <0.07.     

BaMoO4 powders processed in domestic microwave-hydrothermal: Synthesis, characterization and photoluminescence at room temperature

In this paper, BaMoO₄ powders were prepared by the coprecipitation method and processed in a domestic microwave-hydrothermal. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman) spectroscopy, ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. The morphology of these powders were investigated by scanning electron microscopy (SEM). SEM micrographs showed that the BaMoO₄ powders present a polydisperse particle size distribution. XRD and FT-Raman analyses revealed that the BaMoO₄ powders are free of secondary phases and crystallize in a tetragonal structure. UV-vis was employed to determine the optical band gap of this material. PL measurements at room temperature exhibited a maximum emission around 542 nm (green emission) when excited with 488 nm wavelength. This PL behavior was attributed to the existence of intrinsic distortions into the [MoO₄] tetrahedron groups in the lattice.