Preparation, Characterization, and Photocatalytic Activity of N, S-Codoped TiO2 Nanoparticles

The doping of titanium dioxide (TiO₂) with various metal or nonmetal elements has been considered as an effective strategy to extend the photoactive wavelength region to visible light. In this paper (nitrogen [N] and sulfur [S])-codoped anatase TiO₂ nanoparticles were prepared via a sol–gel route, followed by a heat treatment at elevated temperatures. The as-prepared samples were extensively characterized by X-ray diffraction, UV–Vis absorption spectroscopy, and X-ray photoelectron spectroscopy. The N, S-codoped TiO₂ nanoparticles showed a strong visible light absorption and exhibited an enhanced photocatalytic activity for the degradation of methylene blue as compared with the pure, N- or S-doped TiO₂ under either UV light or solar light irradiation.     

CNTs/Ta3N5 Nanocomposite with Enhanced Photocatalytic Activity Under Visible Light Irradiation

Carbon nanotubes (CNTs)/Ta₃N₅ nanocomposite is presented as a novel photocatalyst working under visible light irradiation. The results of Fourier transform infrared analyses and transmission electron microscopy indicate that a good interfacial combination has formed between CNTs and Ta₃N₅ nanoparticles. The CNTs/Ta₃N₅ nanocomposite shows strong absorption in the visible light range compared with pure Ta₃N₅ and has a bandgap energy of 2.01 eV. The photocatalytic experiments show that the nanocomposite has a higher photocatalytic activity than Ta₃N₅ nanoparticles.     

Optical and Photocatalytic Properties of Spinel ZnCr2O4 Nanoparticles Synthesized by a Hydrothermal Route

In this paper, a simple hydrothermal route has been developed to synthesize ZnCr₂O₄ nanoparticles. Experimental results show that the as-prepared ZnCr₂O₄ nanoparticles have an average particle size of <5 nm. The ZnCr₂O₄ nanoparticles have a direct band gap about 3.46 eV and exhibit blue emission in the range of 300–430 nm, centered at 358 nm when excited at 220 nm. Furthermore, the nanoparticles show apparent photocatalytic activities for the degradation of methylene blue under UV light irradiation.     

Low-Temperature Synthesis of YVO4 Nanoparticles and their Photocatalytic Activity

Yttrium orthovanadate (YVO₄) nanoparticles with nearly spherical shape were successfully synthesized via a molten salt method at a low temperature of 200°C. The as-prepared powders were characterized by X-ray diffraction, transmission electron microscopy and UV-Vis spectroscopy, respectively. The results show that increasing salt amount and/or elevating calcining temperature can greatly promote the crystallization and growth of YVO₄ phase. UV-Vis absorption spectra suggested that YVO₄ nanoparticles with the smaller particle size have the stronger UV absorption, and the sequent photocatalytic degradation data also confirmed their higher photocatalytic activity.     

X-Ray, Micro-Raman, Optical Absorption/Emission Studies of ErNbO4 Grown by Vapor Transport Equilibration

Vapor transport equilibration (VTE) treatments were performed on a Y-cut bulk Er (1.6 mol%)-doped congruent LiNbO₃ crystal and an X-cut pure congruent crystal, on one surface of which a 40 nm-thick film of erbium metal was coated before the VTE treatment. Scanning electron microscope, powder or single-crystal X-ray diffraction (XRD), polarized infrared absorption/emission of Er³⁺ as well as micro-Raman spectroscopy were used to study the two VTE crystals. The results are discussed in comparison with a corresponding as-grown bulk Er-doped crystal, calcined ErNbO₄ powder, and a locally Er-doped congruent LiNbO₃ crystal prepared by using the standard Er-diffusion technique. The experimental results show that the VTE treatment induces the formation of micrometer-sized ErNbO₄ precipitates with the crystallographic morphology of a flat polyhedron not only on the surfaces of both crystals but also in the bulk of the homogeneously Er-doped one. The optical absorption and emission studies show that the formation of the precipitates results in substantial spectral changes in both the 0.98 and 1.5 μm regions. The micro-Raman studies allow to resolve four additional Raman peaks around 800 cm⁻¹ in the E(TO) spectra of the two VTE crystals. These additional Raman peaks are associated with the characteristic vibrations with respect to the NbO₄³⁻ group. Characteristic XRD, optical absorption, and emission and Raman peaks for identifying the ErNbO₄ phase are proposed. Finally, the formation mechanism and light-scattering effect of the precipitates are discussed.     

Direct Formation and Photocatalytic Performance of Anatase (TiO2)/Silica (SiO2) Composite Nanoparticles

Anatase (TiO₂)/silica (SiO₂: 23.9–27.7 mol%) composite nanoparticles were directly synthesized from (i) the reaction of titanyl sulfate (TiOSO₄) and sodium metasilicate (Na₂SiO₃) under mild hydrothermal conditions, (ii) the acidic precursor solutions of TiOSO₄ and tetraethylorthosilicate (TEOS) by thermal hydrolysis, and (iii) the metal alkoxides, i.e., tetraisopropoxide (TTIP) and TEOS, by the sol–gel method. Their photocatalytic activities were evaluated by measurements of the relative concentration of methylene blue after UV irradiation. The as-prepared TiO₂/SiO₂ composite nanoparticles showed far more improved photocatalytic activity than the pure anatase-type TiO₂. The composite nanoparticles formed from (i) TiOSO₄ and Na₂SiO₃ as well as those from (ii) TiOSO₄ and TEOS showed fairly good photocatalytic activity, and it was better than that of those synthesized from (iii) the metal alkoxides, which was suggested to be due to the difference in crystallinity of the anatase.     

Photocatalytic Activity of Ni 8 wt%-Doped TiO2 Photocatalyst Synthesized by Mechanical Alloying Under Visible Light

Ni 8 wt%-doped titanium dioxide (TiO₂) was synthesized by mechanical alloying. The photocatalytic activity of Ni 8 wt%-doped TiO₂ powder was evaluated by measuring the visible light absorption ability by ultraviolet visible diffuse reflectance spectroscopy (UV/Vis-DRS) and photoluminescence (PL) spectroscopy. Ni 8 wt%-doped TiO₂ powders had only a rutile phase and spherical particles with an average grain size of less than 10 nm. The UV/Vis-DRS analysis showed that the UV absorption for the Ni 8 wt%-doped TiO₂ powder moved to a longer wavelength and the photoreactivity was rapidly enhanced. And PL results revealed that the new absorption was believed to be induced by localization of the trapping level near the valance band or conduction band. Moreover, Ni 8 wt%-doped TiO₂ had a high reaction activity for decomposition of 4-chlorophenol in aqueous solution under UV and visible light. To obtain the electronic structure of Ni-doped TiO₂, we have performed ab initio pseudopotential plane wave methods based on the density functional theory. The band gap of Ni-doped TiO₂ narrowed more than pure TiO₂. These results agree with the experimentally observed phenomenon.     

Hydrothermal doping method for preparation of Cr-TiO2 photocatalysts with concentration gradient distribution of Cr

Cr³⁺-doped anatase titanium dioxide photocatalysts were prepared by the combination of sol–gel process with hydrothermal treatment. The samples were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area (S_BET), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was confirmed that Cr substitutes Ti⁴⁺ in TiO₂ lattice in trivalent ionic state, and the concentrations of dopants Cr³⁺ decrease from the exterior to the interior of doped TiO₂. The photocatalytic activity of Cr-TiO₂ was investigated for the photocatalytic degradation of XRG aqueous solution both under UV and visible light irradiation. Due to the excitation of 3d electron of Cr³⁺ to the conduction band of TiO₂, Cr-TiO₂ shows a good ability for absorbing the visible light to degrade XRG. Doping of chromium ions effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.15% and 0.2%, respectively. The special distribution of dopants Cr³⁺ seems having a good effect on enhancing the photocatalytic activity of Cr-TiO₂.     

Preparation of NiAl2O4/SiO2 and Co2+-Doped NiAl2O4/SiO2 Nanocomposites by the Sol–Gel Route

NiAl₂O₄/SiO₂ and Co²⁺-doped NiAl₂O₄/SiO₂ nanocomposite materials of compositions 5% NiO – 6% Al₂O₃– 89% SiO₂ and 0.2% CoO – 4.8% NiO – 6% Al₂O₃– 89% SiO₂, respectively, were prepared by a sol–gel process. NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals were grown in a SiO₂ amorphous matrix at around 1073 K by heating the dried gels from 333 to 1173 K at the rate of 1 K/min. The formations of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in SiO₂ amorphous matrix were confirmed through X-ray powder diffraction, Fourier transform infrared spectroscopy, differential scanning calorimeter, transmission electron microscopy (TEM), and optical absorption spectroscopy techniques. The TEM images revealed the uniform distribution of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in the amorphous SiO₂ matrix and the size was found to be ∼5–8 nm.     

SiO2/g-C3N4复合粉体制备及其光催化性能

以Stöber法制备出的二氧化硅(SiO₂)微球和三聚氰胺为原料,两者按一定质量比混合后得到前驱体,通过煅烧该前驱体可成功获得SiO₂/g-C₃N₄复合粉体。利用XRD、SEM、UV-Vis和BET等表征手段对获得的复合粉体进行物相组成、形貌、可见光吸收性能以及比表面积大小等进行分析和测试。结果表明,改进的Stöber法制备出的球形SiO₂平均粒径约为200 nm,具有良好的分散性。SiO₂/g-C₃N₄复合粉体中SiO₂含量约为75%(质量分数)时,其比表面积最大,约为23.7 m²/g。同时,以罗丹明B和亚甲基蓝为目标污染物,在可见光照射下,探究了不同g-C₃N₄负载量SiO₂/g-C₃N₄复合粉体的光催化性能。结果表明,随着复合粉体中g-C₃N₄含量的降低,复合粉体的可见光催化活性反而逐渐升高,g-C₃N₄含量约为25%(质量分数)时复合粉体光催化降解罗丹明B和亚甲基蓝效果最好。原因可归结为,复合粉体的强吸附增强了可见光催化性能。     

Oxygen-Enhanced Crystallization of Solution-Derived 12CaO·7Al2O3

12CaO·7Al₂O₃ (C12A7) composed of nanosize cage structure can clathrate oxygen radicals (O⁻) and has a high potential to application of strong oxidizing catalysis. In the present report, we demonstrate a fabrication route to C12A7 fine powders by Chemical Solution Deposition method in order to enhance the catalytic reactivity. Aluminum sec-butoxide, calcium nitrate tetrahydrate, acetylacetone, 2-methoxyethanol, and nitric acid were used as raw materials. Precursor solution was dried and annealed at 800°–900°C in air or O₂ atmosphere. Crystalline C12A7 powders were obtained by annealing at 900°C in O₂ atmosphere. Scanning electron microscope and transmission electron microscope images of the obtained powders revealed C12A7 particles were sintered and formed several micrometer particles with many pores. BET specific surface area of the powders was 4.2 m²/g. Possibility for synthesizing C12A7 powder with higher specific surface area by the solution process was indicated.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

New Red- and Green-Emitting Phosphors, AYP2O7.5:RE3+ (A=Ca and Sr; RE=Eu and Tb) under Near-UV Irradiation

New red- and green-emitting phosphors, AY_{1− x} P₂O_7.5: x RE³⁺ (A=Ca and Sr; x =0.01, 0.03, 0.05, 0.10; RE=Eu and Tb) were synthesized by the conventional ceramic route and their photoluminescence properties under near-ultraviolet (UV) irradiation were investigated. It was found that CaYP₂O_7.5: Eu³⁺ phosphor emits strong red light when excited by a radiation of 394-nm wavelength and SrYP₂O_7.5:Eu³⁺ gives intense orange light when excited by a radiation of 396-nm wavelength. Strong green emission for AY_{1− x} P₂O_7.5:Tb³⁺ is also observed under near-UV irradiation (378 nm). When compared with emission intensity from a standard YPO₄:0.05Tb³⁺, the emission from SrYP₂O_7.5:0.05Tb³⁺ showed greater intensity values under the same excitation wavelength (378 nm). X-ray powder diffraction analysis showed that AYP₂O_7.5 has xenotime-type structure.     

Fabrication and Luminescent Properties of Nd3+-Doped Lu2O3 Transparent Ceramics by Pressureless Sintering

The fabrication of transparent Nd³⁺ ion-doped Lu₂O₃ ceramics is investigated by pressureless sintering under a flowing H₂ atmosphere. The starting Nd-doped Lu₂O₃ nanocrystalline powder is synthesized by a modified coprecipitant processing using a NH₄OH+NH₄HCO₃ mixed solution as the precipitant. The thermal decomposition behavior of the precipitate precursor is studied by thermogravimetric analysis and differential thermal analysis. After calcination at 1000°C for 2 h, monodispersed Nd³⁺:Lu₂O₃ powder is obtained with a primary particle size of about 40 nm and a specific surface area of 13.7 m²/g. Green compacts, free of additives, are formed from the as-synthesized powder by dry pressing followed by cold isostatic pressing. Highly transparent Nd³⁺:Lu₂O₃ ceramics are obtained after being sintered under a dry H₂ atmosphere at 1880°C for 8 h. The linear optical transmittance of the polished transparent samples with a 1.4 mm thickness reaches 75.5% at the wavelength of 1080 nm. High-resolution transmission electron microscopy observations demonstrate a "clear" grain boundary between adjacent grains. The luminescent spectra showed that the absorption coefficient of the 3 at.% Nd-doped Lu₂O₃ ceramic at 807 nm reached 14 cm⁻¹, while the emission cross section at 1079 nm was 6.5 × 10⁻²⁰ cm².     

Synthesis of Nanosized Titanium-Chromium Oxynitride Powders by Ammonolysis of Coprecipitated TiO2/Cr2O3 Precursors

Interstitial titanium-chromium oxynitrides in the solid solution series Ti_{1− z} Cr _z (O _x N _y ) ( z = 0.2, 0.4, 0.5, 0.6, 0.8) have been obtained by ammonolysis of the TiO₂/Cr₂O₃ precursors resulting from the coprecipitation method. The precursors and the resulting oxynitrides were characterized by auger electron spectroscopy, X-ray diffraction analysis, electron probe microanalysis, transmission electron microscopy, and BET surface area techniques. Compounds in the Ti_{1− z} Cr _z (O _x N _y ) series are prepared as single phases by nitridation at 1073 K for 8 h. The as-synthesized oxynitride powders contain only Ti_{1− z} Cr _z (O _x N _y ) with cubic structure and the particle size is in the nanometer scale.     

Synthesis of Nanosize-Necked Structure α- and γ-Fe2O3 and its Photocatalytic Activity

Highly dispersed nanometer-sized α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite) iron oxide particles were synthesized by the combustion method. Ferric nitrate was used as a precursor. X-ray diffractometer study revealed the phase purity of α- and γ-Fe₂O₃. Both the products were characterized using field emission scanning electron microscope and transmission electron microscope for particle size and morphology. Necked structure particle morphology was observed for the first time in both the iron oxides. The particle size was observed in the range of 25–55 nm. Photodecomposition of H₂S for hydrogen generation was performed using α- and γ-Fe₂O₃. Good photocatalytic activity was obtained using α- and γ-Fe₂O₃ as photocatalysts under visible light irradiation.     

Preparation and Physical Properties of Radiofrequency-Sputtered Amorphous Films in the System AlPO4–TiO2

Amorphous films in the system AlPO₄–TiO₂ were prepared by an rf-sputtering method, and their physical properties, such as density, refractive index, and thermal expansion coefficient, and the infrared absorption spectra were measured. The thermal expansion coefficient increased linearly with increasing TiO₂ content. The results of the molar refractivity and the infrared absorption spectra indicated that the coordination number of titanium ions in these films is higher than that in SiO₂–TiO₂ glasses with a negative thermal expansion, in which Ti⁴⁺ ions are tetrahedrally coordinated. In order to confirm the coordination state of the titanium ions in these amorphous films, titanium K -band emission spectra were obtained by X-ray emission spectroscopy, revealing sixfold coordination. The higher coordination state of Ti⁴⁺ was considered to account for these amorphous films not exhibiting negative thermal expansion, as in the SiO₂–TiO₂ system.     

Preparation and Characterization of High-Purity HfTiO4

The double decomposition of hafnium and titanium tetrakis tertiary amyloxides was used to produce high-purity stoichiometric submicron HfTiO₄ powders. The particle size range was 50 to 400 Å. X-ray diffraction of a 1:1 mixture, as-prepared and heated to ∼750°C, indicated that the material is 95% orthorhombic HfTiO₄. The TGA, BET, DTA, and high-temperature X-ray analysis of the as-prepared powders are also reported; the ir absorption and reflection frequencies of HfTiO₄ were determined. The homogeneity and stoichiometry of the powder were demonstrated by electron microscopy and wet chemical analysis. Mixed oxides prepared in this manner were sintered in an ambient atmosphere at 1650° to 1700°C for 4 h or Ionger into a body of nearly theoretical density and uniform microstructure.     

Sol–Gel Synthesis and Photocatalytic Activity of CeO2/TiO2 Nanocomposites

Uniform CeO₂ / TiO₂ composite nanoparticles with different Ce/Ti molar ratios have been successfully synthesized via the sol–gel method. The samples were characterized using differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The surface state analysis by means of X-ray photoelectron spectroscopy (XPS) shows that the Ti element mainly exists as a chemical state of Ti⁴⁺, while the Ce element exists as a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. The photocatalytic degradation of methyl orange (MeO) in CeO₂ / TiO₂ suspension was investigated. The results indicate that the CeO₂/TiO₂ nanocomposites show higher photocatalytic activity than pure TiO₂. Photodegradation of MeO can be improved by increasing the Ce/Ti molar ratio in the initial 15 min.     

Visible-light photocatalytic activity of TiO2/ZnS nanocomposites prepared by homogeneous hydrolysis

Photocatalytic active TiO₂/ZnS composites were prepared by homogeneous hydrolysis of mixture of titanium oxo-sulphate and zinc sulphate in aqueous solutions with thioacetamide. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission microscopy (HRTEM) and electron diffraction (ED). The nitrogen adsorption–desorption was used for surface area (BET) and porosity determination. Diffuse reflectance UV/VIS spectra for evaluation of photophysical properties were recorded in the diffuse reflectance mode (R100) and transformed to an absorption spectra through the Kubelka–Munk function. The method of UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies of the prepared TiO₂/ZnS nanocomposites. The photoactivity of the prepared TiO₂/ZnS nanocomposites was assessed by the photocatalytic decomposition of Orange II dye in an aqueous slurry under irradiation of 255 nm, 365 nm and 400 nm wavelength. Under the same conditions, the photocatalytic activity of the commercially available photocatalyst (Degussa P25), the pure anatase TiO₂ and sphalerite ZnS were also examined. The composite sample having the highest catalytic activity was obtained by hydrolysis of mixture solutions 0.63 M TiOSO₄ and 0.08 M ZnSO₄ · 7H₂O.