Synthesis of titanium dioxide with oxygen vacancy and its visible-light sensitive photocatalytic activity

A novel active carbon reducing process was developed for the synthesis of titanium dioxide with oxygen vacancy. In this process a nanocomposite of hydrolyzed titanium(IV) tetra-isopropoxide and the active carbon was annealed in air. The formation reaction, visible-light absorption, and visible-light sensitive photocatalytic activity of the titanium dioxide with oxygen vacancy samples were investigated using XRD, TG-DTA analyses, FE-SEM, EDS, and measurements of electric conductivity, BET specific surface area and photocatalytic activity. The nonstoichiometric titanium dioxide with oxygen vacancy sample has a rutile structure and its chemical formula can be written as Ti(IV)_1−xTi(III)_xO_(2−x/2)□_x/2, where □ is oxygen vacancy. The oxygen vacancy was introduced into the rutile structure by reducing reaction of the active carbon in a phase transformation process from anatase to rutile. The samples showed visible-light absorption with an absorption edge around 570 nm and high surface visible-light sensitive photocatalytic activity.     

TiO2 supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

TiO₂ nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N₂-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO₂/SBA-15 composite was prepared by loading TiO₂ nanoparticles on uniform rod-like SBA-15 of 1 μm length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.     

Ligand-assisted hydrothermal synthesis of ZnWO4 rods and their photocatalytic activities

ZnWO₄ rods were prepared using a ligand-assisted hydrothermal method with ZnCl₂ and Na₂WO₄ in the presence of various amines as ligands for zinc ions. The choice of ligand was found to play an important role in the formation of ZnWO₄ rods. The aspect ratio of the ZnWO₄ rods increased with increasing ligand strength. XRD and HRTEM confirmed that the ZnWO₄ rods grow along the [1 0 0] direction. The photochemical activities of the ZnWO₄ rods for the decomposition of Rhodamine 6G were examined. The photocatalytic activity was found to depend on the aspect ratio of the ZnWO₄ rods.     

Synthesis of nanocrystalline Mo2C via sodium co-reduction of MoCl5 and CBr4 in benzene

Molybdenum carbide (Mo₂C) has been synthesized via a sodium co-reduction of molybdenum pentachloride (MoCl₅) and carbon tetrabromide (CBr₄) in benzene at 350 °C for 12 h. X-ray diffraction (XRD) pattern indicated that the product was mainly hexagonal Mo₂C with a small amount of cubic Mo₂C. The lattice constants of the hexagonal Mo₂C were a=3.009 and c=4.736 Å. Transmission electron microscopy (TEM) study showed that the product consisted of slightly conglomerated particles of about 30 nm in size.     

Synthesis and enhanced photocatalytic activity of tin oxide nanoparticles coated on multi-walled carbon nanotube

A nanocomposite of SnO₂ nanoparticles coated on multi-walled carbon nanotube (MWNT@SnO₂) was synthesized and characterized by thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, nitrogen physisorption measurements, photoluminescence. The results show that the SnO₂ nanoparticles with a narrow size of 4 nm are uniformly deposited on MWNT. The photocatalytic activity of the nanocomposite was studied using methyl orange as a model organic pollutant. MWNT@SnO₂ exhibits much higher photocatalytic activity than that of commercial TiO₂ (P-25). The promotion is mainly contributed from electron transfer between SnO₂ and MWNT.     

Si-substituted hydroxyapatite nanopowders: Synthesis, thermal stability and sinterability

Synthetic hydroxyapatites incorporating small amounts of Si have shown improved biological performances in terms of enhanced bone apposition, bone in-growth and cell-mediated degradation.This paper reports a systematic investigation on Si-substituted hydroxyapatite (Si 1.40 wt%) nanopowders produced following two different conventional wet methodologies: (a) precipitation of Ca(NO₃)₂·4H₂O and (b) titration of Ca(OH)₂. The influence of the synthesis process on composition, thermal behaviour and sinterability of the resulting nanopowders is studied.Samples were characterised by electron microscopy, induced coupled plasma atomic emission spectroscopy, thermal analysis, infrared spectroscopy, N₂ adsorption measurements, X-ray diffraction and dilatometry. Semicrystalline Si-substituted hydroxyapatite powders made up of needle-like nanoparticles were obtained, the specific surface area ranged between 84 and 110 m²/g. Pure and Si-substituted hydroxyapatite nanopowders derived from Ca(NO₃)₂·4H₂O decomposed around 1000 °C. Si-substituted hydroxyapatite nanopowders obtained from Ca(OH)₂ were thermally stable up to 1200 °C and showed a distinct decreased thermal stability with respect to the homologous pure sample. Si-substituted hydroxyapatites exhibited higher sintering temperature and increased total shrinkage with respect to pure powders. Nanostructured dense ceramics were obtained by sintering at 1100 °C Si-substituted hydroxyapatites derived from Ca(OH)₂.     

A simple route to prepare nanocrystalline titanium carbonitride

Nanocrystalline titanium carbonitride, TiC_0.7N_0.3, has been synthesized directly by a simple reaction route of TiCl₄ and C₃N₃C1₃ using sodium as the reductant at 600°C. The composition of the powders has been investigated by X-ray powder diffraction. Transmission electron microscopy image reveals that the average size of the obtained particles is about 30 nm.     

Preparation, characterization, and stability of calcium zinc hydrophosphate

Calcium zinc hydrophosphate phases with different Zn/(Zn + Ca) molar ratios (x_Zn, from 0 to 1) were synthesized using co-precipitation method at pH 10, 25 °C. X-ray diffraction, FT-IR spectroscopy and field emission scanning electron microscopy (FE-SEM) were used to characterize the synthesized products. Thermal behavior of the products was examined by thermal analytical instruments (TG-DSC-MS), while the chemical stability of the products was tested by toxicity characteristic leaching procedure (TCLP).The results showed that the phase constituents of formed calcium zinc hydrophosphate phases were related to the molar contents of Zn²⁺. With the increase of x_Zn, it formed calcium-deficient hydorxyapatite (CaHap), calcium zinc hydorxyapatite (CaZnHap), CaZn₂(PO₄)₂·2H₂O, and Zn₃(PO₄)₂·4H₂O, respectively. All the calcium zinc hydrophosphates were thermally stable up to 600 °C, and less Zn²⁺ leached in a wide pH range of 2-11, which indicated that calcium zinc hydrophosphate could effectively hold Zn²⁺ in their crystal phases with stabilization ratios of over 99.99%.     

Self-assembled Cu2O flowerlike architecture: Polyol synthesis, photocatalytic activity and stability under simulated solar light

Self-assembled Cu₂O flowerlike architecture has been synthesized by polyol process with the presence of acetamide. The synthesized flowerlike architecture is composed of the petals assembled by small crystalline with size of 5-6 nm. The growth mechanism is proposed that the dissolution of the small particles in microsphere center and then the recrystallization on the surface of the microspheres with the increase of reaction time results in the formation of the final flowerlike architecture. The novel architecture shows a blue shift of absorption edge compared to Cu₂O nanocubes and good photocatalytic activity for the degradation of dye brilliant red X-3B under simulated solar light. Moreover, the flowerlike architecture is more stable than Cu₂O nanocubes during photocatalytic process since the photocatalytic activity of the second reused architecture sample is still twice as high as that of the original nanocubes. The Cu₂O flowerlike architecture may be a good photocatalyst candidate for wastewater treatment.     

Route to transition metal carbide nanoparticles through cyanamide and metal oxides

We have designed an efficient route to the synthesis of transition metal carbide nanoparticles starting from an organic reagent cyanamide and transition metal oxides. Four technologically important metal carbide nanoparticles such as tungsten carbide, niobium carbide, tantalum carbide and vanadium carbide were synthesized successfully at moderate temperatures. It is found that cyanamide is an efficient carburization reagent and that the metal oxides are completely transmitted into the corresponding carbide nanoparticles. A possible mechanism is proposed to explain the results of the reaction between cyanamide and the metal oxides.     

Structural stability and mutual transformations of molybdenum carbide, nitride and phosphide

The structural stability and transformations of Mo carbide, nitride and phosphide were investigated under various atmosphere conditions by X-ray diffraction (XRD). The results indicated that the order of structural stability of these Mo-based compounds was as follows: Mo₂N < Mo₂C < MoP. Both Mo₂C and Mo₂N can be transformed to MoP, whereas the reverse transformations did not occur. Noticeably, compared with those Mo sources containing oxygen, the use of Mo₂C/Mo₂N as Mo-source can produce finely dispersed MoP nanoparticles by the temperature-programmed reaction (TPR) method. The result was probably due to the fact that lower-levels H₂O generated during synthesis process can avoid strong hydrothermal sintering. The influence of formation energy had been considered and was found to relate to the structural stability and transformations of these Mo-based compounds.     

Iron-stabilized nanocrystalline ZrO2 solid solutions: Synthesis by combustion and thermal stability

The synthesis of Fe³⁺-stabilized zirconia by the nitrate/urea combustion route was investigated. Using several characterization techniques, including X-ray diffraction, field-emission-gun scanning electron microscopy and notably Mössbauer spectroscopy, it was possible to determine the appropriate amount of urea that allows to obtain a totally stabilized Zr_0.9Fe_0.1O_1.95 solid solution. The nanocrystalline zirconia solid solution is mostly tetragonal, but the presence of the cubic phase could not be ruled out. An in-depth study of the thermal stability in air showed that the Fe³⁺ solubility in the stabilized solid solution starts to decrease at about 875 °C which results in the formation of hematite (possibly containing some Zr⁴⁺) at the surface of the zirconia grains and further provokes the progressive transformation into the monoclinic zirconia phase.     

Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO₃H-MCM-41-NH₂. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state ¹³C CP/MAS NMR and solid-state ²⁹Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO₃H-MCM-41-NH₂) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.     

Phase selection and visible light photo-catalytic activity of Fe-doped TiO2 prepared by the hydrothermal method

It is necessary to extend the absorption range of TiO₂ based materials from the ultraviolet to the visible light region for most photo-catalytic applications of TiO₂ under solar irradiance or indoor lighting. Also, the ability to control the structural evolution, particularly the competition and transformation between different phases (anatase or rutile), is extremely important for the preparation of high efficiency TiO₂ based photo-catalysts. In this work, we have systematically studied the effects of various processing factors on the phase selection process/outcome of nanocrystalline Fe-doped TiO₂, which includes the level of doping ions, annealing temperature, solution pH and the addition of acidic anions, using a low temperature hydrothermal method. Both Fe-doped rutile and anatase TiO₂ phases were obtained via varying the processing conditions. The visible-light photo-catalytic activity of doped materials was significantly improved over that of the pure TiO₂ nanopowders, which was demonstrated by effective degradation of methylene blue under visible light.     

Synthesis of alumina supported LaMnO3 with excellent thermal stability by a PVP-assisted route

LaMnO₃/Al₂O₃ catalysts were successfully prepared by a novel method with polyvinyl pyrrolidone (PVP) as complexant and characterized by XRD, TGA, IR, BET, XPS and TEM techniques. The TGA and IR characterizations of the precursor revealed that LaMnO₃ structure was formed under mild conditions without combustion of any organic compounds. The obtained catalysts exhibited better activity for methane combustion than those prepared by citrate method, mainly due to larger pore volume, more active oxygen species on surface and the formation of a pure perovskite structure. The high surface area of about 122 m² g⁻¹ was retained even after calcined at 1000 °C; and interestingly, no phase transformation or solid-state reaction was observed. This fact indicated the excellent thermal stability of catalysts, which was ascribed to the strong interaction between the support and active phase.     

Effects of pH on morphosynthesis and photocatalytic activity of calcium titanium oxides via a facile aqueous strategy

By controlling pH values, calcium titanium oxides with various morphologies had been synthesized via a simple hydrothermal route. No surfactants or templates were involved in the shaping process. The results found that pH values had a crucial effect on the crystal phase and shape evolution of the samples. With increasing pH values, the obtained sample changed from one-dimension (1D) CaTi₂O₅ rod or shuttle-like shape to two-dimension (2D) CaTi₂O₄(OH)₂ nanosheets, and then to three-dimension (3D) CaTiO₃ aggregated prisms, butterfly-like dendrites and cross cubic shapes. The formation mechanism was proposed for the evolution of phase and morphology. 3D CaTiO₃ butterfly-like sample showed good photocatalytic activity due to unique morphology, enhanced light harvesting and large surface area.     

Preparation and electrocatalytic activity of tungsten carbide and titania nanocomposite

Tungsten carbide and titania nanocomposite was prepared by combining a reduced-carbonized approach with a mechanochemical approach. The samples were characterized by X-ray diffraction, transmission electron microscope under scanning mode and X-ray energy dispersion spectrum. The results show that the crystal phases of the samples are composed of anatase, rutile, nonstoichiometry titanium oxide, monotungsten carbide, bitungsten carbide and nonstoichiometry tungsten carbide, and they can be controlled by adjusting the parameters of the reduced-carbonized approach; tungsten carbide particles decorate on the surface of titania support, the diameter of tungsten carbide particle is smaller than 20 nm and that of titania is around 100 nm; the chemical components of the samples are Ti, O, W and C. The electrocatalytic activity of the samples was measured by a cyclic voltammetry with three electrodes. The results indicate that the electrocatalytic activities of the samples are related to their crystal phases and the property of electrolyte in aqueous solution. A synergistic effect between titania and tungsten carbide is reported for the first time.     

Photocatalytic activity of nitrogen doped rutile TiO2 nanoparticles under visible light irradiation

This work provides the design and synthesis of nitrogen doped rutile TiO₂ nanoparticles working as efficient photocatalysts under visible light irradiation. Nitrogen doped rutile TiO₂ nanoparticles are synthesized through the surface nitridation of rutile nanoparticles, which have been prepared in advance. The experimental results show that the nitrogen element is easily doped into the lattice of TiO₂ nanoparticles and its doping amount increases with the decrease of nanocrystallite size. The photocatalytic activity of the nanoparticles under visible light irradiation is correlated not only with the amount of doped nitrogen element but also with the morphology and crystallinity of nanoparticles.     

Controlled synthesis of anatase TiO2 octahedra with enhanced photocatalytic activity

Titanium dioxide (TiO₂) nanocrystals with specific exposed crystal facet have attracted considerable interest due to their promising applications in the fields of energy and environment. In this paper, we report on a simple solvothermal approach for the synthesis of anatase TiO₂ octahedra with high yield, using titanium(IV) sulfate and hydrazine hydrate as the starting materials. The formation mechanism of anatase TiO₂ octahedra is suggested. The samples were characterized with XRD, Raman, SEM, TEM, FTIR, XPS, and UV/vis techniques, and further tested as a candidate in photocatalysis to decompose methyl orange in aqueous solution at room temperature. The results show that SO₄²⁻ ions not only benefit the formation of octahedral nanocrystals, but also inhibit nitrogen doping into TiO₂ matrix. More importantly, it is found that the octahedral TiO₂ nanocrystals show enhanced photocatalytic activity compared to TiO₂ P25 and anatase TiO₂ counterparts.     

Preparation and characterization of Cu2O-TiO2: Efficient photocatalytic degradation of methylene blue

A series of copper-deposited titania were prepared by photoreduction method under irradiation with a 125-W high-pressure mercury lamp. From XPS and AES results, the deposited-copper formed Ti-O-Cu bond on the surface of TiO₂, and the Cu species on the surface of copper-deposited TiO₂ can be identified as Cu(I). The photocatalytic degradation activity of methylene blue for the Cu₂O-TiO₂ series increased with increasing Cu₂O-deposited content, and then decreased. The highest photocatalytic degradation activity of methylene blue was obtained for 0.16% Cu₂O-TiO₂. When copper-deposited content reached to 0.32%, the photocatalytic activity was lower than that of pure TiO₂. It is shown that Cu₂O on the surface of TiO₂ can trap electrons from the TiO₂ conduction band, and the electrons trapped on the Cu₂O-TiO₂ site are subsequently transferred to the surrounding adsorbed O₂, thereby avoiding electron-hole recombination, and enhancing the photocatalytic activity. Excess copper loading may screen the photocatalyst from the UV source, so the photocatalytic activity diminishes with increasing Cu₂O.