Influence of morphology and surface characteristics on the photocatalytic activity of rutile titania nanocrystals

This article presents the synthesis of phase-pure rutile titania with different morphologies via hydrothermal method at significantly low temperatures (40-150 °C) without any additives and their application as efficient photocatalyst for environmental remediation. Phase and morphology has been determined with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ultra violet diffuse reflectance spectroscopy (UV-DRS) shows the optical band-gap in the range of ∼2.8-3.1 eV and Brunauer-Emmett-Teller specific surface area is found to be between 70 and 140 m²/g depending on the synthesis conditions. Raman spectroscopic analyses of the samples provide valuable insights into the structural and stoichiometric details. Photodegradation of the pollutant azo-dye, methyl orange (MO) in presence and absence of oxygen was performed to study the photocatalytic efficiency of the synthesized materials. Complete photodegradation of the dye is confirmed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) study. Dependence of dye photodegradation rate on morphology, specific surface area, surface nonstoichiometry and acidity were investigated in detail. Catalyst performance was compared from the rate constants obtained for each reaction using non-linear least square fitting (NLSF) to the experimental data in a concentration ratio (C₀/C_t) versus time (t) plot which shows extraordinarily high activity for all samples compared to commercial reference. Among them the catalyst synthesized at 40 °C for 16 h showed best activity. Kinetic study of the reaction matches well with simulated fit to experimental data and confirms to be pseudo-first order reaction.     

Adsorption of vitamin E on mesoporous titania nanocrystals

Tri-block nonionic surfactant and titanium chloride were used as starting materials for the synthesis of mesoporous titania nanocrystallite powders. The main objective of the present study was to examine the synthesis of mesoporous titania nanocrystals and the adsorption of vitamin E on those nanocrystals using X-ray diffraction (XRD), transmission electron microscopy, and nitrogen adsorption and desorption isotherms. When the calcination temperature was increased to 300 °C, the reflection peaks in the XRD pattern indicated the presence of an anatase phase. The crystallinity of the nanocrystallites increased from 80% to 98.6% with increasing calcination temperature from 465 °C to 500 °C. The N₂ adsorption data and XRD data taken after vitamin E adsorption revealed that the vitamin E molecules were adsorbed in the mesopores of the titania nanocrystals.     

Room temperature synthesis of nearly monodisperse rodlike rutile TiO2 nanocrystals

A new method was developed to synthesize uniform rodlike rutile TiO₂ nanocrystals by the hydrolysis of tetrabutyl titanate [Ti(OC₄H₉)₄] in hydrochloric acid-alcohol aqueous solutions at room temperature. The hydrolytic sol-gel reaction generated 44 nm (diameter) × 200 nm (length) sized rutile TiO₂ nanocrystals. Transmission electron microscopic images showed that the particles have a uniform shape and narrow size distribution. X-ray diffraction and electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the rodlike TiO₂ nanoparticles prepared at room temperature were crystalline rutile structure grown along the [001] direction. The morphology and photocatalytic activity of the TiO₂ nanocrystals formed at different urea concentrations were showed. The rutile TiO₂ nanocrystals formed in the absence of urea exhibited higher photocatalytic activity than the commercial photocatalyst P25 on the photocatalytic degradation of Rhodamine B.     

Microwave synthesis of phase-pure, fine silicon carbide powder

Fine, monophasic silicon carbide powder has been synthesized by direct solid-state reaction of its constituents namely silicon and carbon in a 2.45 GHz microwave field. Optimum parameters for the silicon carbide phase formation have been determined by varying reaction time and reaction temperature. The powders have been characterized for their particle size, surface area, phase composition (X-ray diffraction) and morphology (scanning electron microscope). Formation of phase-pure silicon carbide can be achieved at 1300 °C in less than 5 min of microwave exposure, resulting in sub-micron-sized particles. The free energy values for Si + C → SiC reaction were calculated for different temperatures and by comparing them with the experimental results, it was determined that phase-pure silicon carbide can be achieved at around 1135 °C.     

The effects of synthesis procedures on the structure and morphology of multiwalled carbon nanotubes (MWNTs)/titania (TiO2) nanocomposites prepared by hydrothermal method

The nanocomposites of multiwalled carbon nanotubes (MWNTs)/titania (TiO₂) were prepared by direct growth of TiO₂ nanocrystals onto carboxyl-modified MWNTs under hydrothermal condition. The structure and morphology of TiO₂ nanocrystals growing on MWNTs were tuned by adjusting acidity, reaction temperature, and reactant ratio. The results showed that a uniform layer of anatase TiO₂ nanocrystals on MWNTs could be achieved at proper synthesis parameters. Flowerlike assemblage of rutile TiO₂ nanocrystals was dispersed on MWNTs. The formation mechanism of MWNTs/TiO₂ nanocomposites was further provided.     

Variable temperature in situ X-ray diffraction study of mechanically activated synthesis of calcium titanate, CaTiO3

The effect of mechanical activation on formation of calcium titanate (CaTiO₃) from calcined mixtures of CaCO₃ and TiO₂ was studied by monitoring the course of this solid-state reaction by variable temperature in situ X-ray diffraction (XRD) experiments, scanning electron microscopy (SEM) and dilatometry. Two equimolar mixtures of powdered CaCO₃ and TiO₂ were prepared: one was mechanically activated by grinding in a high energy vibro-mill. A total of 32 X-ray diffraction data sets for each sample, collected between 30 and 1100 °C, were analyzed by multiphase Rietveld refinement. Quantitative phase analysis and microstructure analysis obtained from X-ray diffraction are correlated to results of scanning electron microscopy and dilatometry. In the non-activated sample, small quantities of the reactants remain in the product until 1100 °C. In the activated sample, the reaction results in pure CaTiO₃ at 920 °C.     

Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering

Microstructure and hydrophilicity of nano-titanium dioxide (TiO₂) thin films, deposited by radio frequency magnetron sputtering, annealed at different temperatures, were studied by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle methods. It is found that the crystal phase transforms from amorphous to rutile structure with increase of annealing temperature from room temperature to 800 °C. It is also indicated that the organic contaminants on the surface of the films can be removed and the oxygen vacancies can be reduced by the annealing treatment. Annealed at the temperature below 300 °C, amorphous TiO₂ thin films show rather poor hydrophilicity, and annealed at the temperature range from 400 to 650 °C, the super hydrophilicity anatase of TiO₂ thin films can be observed. However, when the annealing temperature reaches 800 °C, the hydrophilicity of the films declines mainly derived from the appearance of rutile.     

Mass-synthesized anatase titania nanocrystals with tunable size and shape via sol-gel in organic solvents with adsorbing ligands

High-quality anatase titania (TiO₂) nanoparticles, nanowires, and nanorods have been mass-synthesized by the modified sol-gel method in the saturated fatty alcohol, acid, and amine systems with adsorbing ligands, respectively. These obtained quasi-spherical TiO₂ nanoparticles showed the mean size of 16.5 nm with a narrow size-distribution. These resulting TiO₂ nanowires had the uniform diameter of 3.8 nm with the length range of 80-180 nm, and TiO₂ nanorods had the uniform diameter of 7.5 nm with the length range of 40-70 nm, respectively. We demonstrated that the shapes, sizes and morphology of these anatase TiO₂ nanocrystals could be controlled systematically by adjusting certain reaction parameters, such as the kind of organic solvents, the alkyl length of organic solvents, and the reaction time. It has been found that the shape of the products was primarily determined by the kind of organic solvents. However, their sizes, size-distributions, and morphology could be controlled by adjusting the alkyl length of organic solvents and the reaction time. Based on the analysis of all experiment results, we have investigated the growth mechanism of these TiO₂ nanocrystals with the different shape. Meanwhile, this synthetic method can be extended further for the preparation of other oxides nanocrystals.     

Hydrothermal preparation, characterization and property research of flowerlike ZnO nanocrystals built up by nanoflakes

In the present paper, flowerlike ZnO nanocrystals were successfully synthesized via a simple hydrothermal route in the presence of sodium dodecyl sulfate (SDS), employing Zn(CH₃COO)₂ and KOH as the starting reactants. The phase and morphology of the product were characterized by means of powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and select area electron diffraction (SAED). The optical properties of the product were studied. Some factors influencing the morphology of the final product including reaction time, temperature and amounts of the surfactant were discussed. Researches showed that the flowerlike ZnO nanocrystals had a good photo-catalytic activity for degradation of safranine T under 254 nm UV light irradiation. The electrochemical research of the product showed that flowerlike ZnO nanocrystals could promote electron transfers between catechol and the Au electrode. A possible formation mechanism was also suggested based on the results of the experiments.     

Low temperature molten salt synthesis of SrTiO3 submicron crystallites and nanocrystals in the eutectic NaCl-KCl

An eutectic NaCl-KCl molten salts method has been developed for the synthesis of SrTiO₃ submicron crystallites and nanocrystals from SrO₂ and two kinds (submicron and nano-sized) of TiO₂ powders at 700 °C, which was much lower than that (generally > 1000 °C) of the conventional solid state reactions. The characterization results from X-ray diffraction and X-ray photoelectron spectroscopy revealed that the obtained products were pure perovskite phase SrTiO₃ without any contamination of Na, K, and Cl ions. The scanning electronic microscopy and transmission electron microscopy images disclosed that the starting TiO₂ played an important role in the morphology and size of the obtained SrTiO₃: while the product derived from TiO₂ submicron crystallites comprised faceted submicron crystallites of about 95-184 nm, that derived from TiO₂ nanocrystals comprised quadrate nanocrystals of about 20-61 nm. Besides, based on the experiments without the molten NaCl-KCl eutectic, at different temperatures and times, and using different kinds of TiO₂, the possible formation mechanism of SrTiO₃ submicron crystallites and nanocrystals was proposed.     

Synthesis of potassium hexatitanate whiskers starting from metatitanic acid and potassium carbonate and sulfate by calcination method

Potassium hexatitanate whiskers were synthesized starting from metatitanic acid (H₂TiO₃), potassium carbonate and sulfate by calcination method. The effects of mole ratios of K₂CO₃ to metatitanic acid (H₂TiO₃), content of potassium sulfate, and calcination temperature on the crystallinity and morphology of the resultant potassium titanate whiskers were investigated by X-ray diffraction and scanning electron microscopy. Well crystallized potassium hexatitanate whiskers with an average length of 7.3 μm and an average diameter of 0.62 μm were synthesized when the molar ratio of K₂CO₃ to metatitanic acid was kept at 1:3.5 and the calcination temperature was up to 1150 °C. The presence of K₂SO₄ favored the formation of thin potassium hexatitanate whiskers as compared to the absence of K₂SO₄. The whiteness and brightness of the synthesized potassium hexatitanate whiskers were comparable to that of rutile TiO₂ pigment.     

Studies on nitrogen modified TiO2 photocatalyst prepared in different conditions

Nitrogen modified titania photocatalysts (TiO₂/N) were characterized using high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), dynamic light scattering (DLS), Raman spectroscopy and BET surface area method. The presence of nitrogen in modified photocatalysts has been studied using FT-IR and XPS analyses. The influence of the calcination temperature in the range of 100-350 °C on nanocrystallite as well as particle size of the samples and their photocatalytic activity was investigated. The calcination of TiO₂/N samples caused a growth of the particle size and an increase of their crystallinity. TEM studies present changes of the diameter and shape of TiO₂ particles and nanocrystallites. The XRD and the Raman response of the samples confirmed an increase of the crystallinity of the samples when annealed at higher temperatures.The photocatalytic activity of the modified photocatalysts was determined using the reaction of phenol decomposition. It was shown that phenol decomposition rate was greatly influenced by pH of the solution. The highest phenol degradation using all the modified samples was observed for pH 7.1 which is close to the PZC point established for pristine TiO₂ at pH 6.8.     

Photoluminescence from terbium doped silica-titania prepared by a sol-gel method

Terbium doped (0.5 at.%) TiO₂-SiO₂ (30%/70%) was prepared by a sol-gel method. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the powder calcined at two different temperatures. At a low temperature of 550 °C an amorphous phase was obtained, but at a higher temperature of 1000 °C, the anatase TiO₂ phase was crystallized in the amorphous SiO₂ phase. Green photoluminescence from ultraviolet excitation was detected after heating to either temperature, but the amorphous sample heated to 550 °C exhibited a higher intensity. X-ray diffraction and photoluminescence excitation data are discussed to explain these observations.     

Green hydrothermal synthesis and optical absorption properties of ZnO2 nanocrystals and ZnO nanorods

A green hydrothermal method was proposed for the controllable synthesis of ZnO₂ nanocrystals and ZnO nanorods, using the common and cost-effective 2ZnCO₃·3Zn(OH)₂ powder and 30 mass% H₂O₂ aqueous solution as the raw materials. The characterization results from X-ray diffraction, high resolution transmission electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the products synthesized at 100-120 °C for 6 h or at 170 °C for 0 h were cubic phase ZnO₂ nanocrystals; while those synthesized at 170 °C for 3-6 h were hexagonal phase ZnO nanorods. The UV-vis absorption spectra showed that the as-synthesized ZnO₂ nanocrystals and ZnO nanorods had optical band gaps of about 4.1 and 3.3 eV, respectively.     

Template-free synthesis of ZnWO4 powders via hydrothermal process in a wide pH range

ZnWO₄ powders with different morphologies were fabricated through a template-free hydrothermal method at 180 °C for 8 h in a wide pH range. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible and luminescence spectrophotometers were applied to study the effects of pH values on crystallinity, morphology, optical and luminescence properties. The XRD results showed that the WO₃ + ZnWO₄, ZnWO₄, and ZnO phases could form after hydrothermal processing at 180 °C for 8 h with the pH values of 1, 3-11, and 13, respectively. The SEM and TEM observation revealed that the morphological transformation of ZnWO₄ powders occurred with an increase in pH values as follows: star anise-, peony-, and desert rose-like microstructures and soya bean- and rod-like nanostructures. The highest luminescence intensity was found to be in sample consisting of star anise-like crystallites among all the samples due to the presence of larger particles with high crystallinity resulted from the favorable pH under the current hydrothermal conditions.     

Hydrothermal synthesis and characterization of TiO2 nanorod arrays on glass substrates

Large-scale, well-aligned single crystalline TiO₂ nanorod arrays were prepared on the pre-treated glass substrate by a hydrothermal approach. The as-prepared TiO₂ nanorod arrays were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. X-ray diffraction results show that the main phase of TiO₂ is rutile. Scanning electron microscopy and transmission electron microscopy results demonstrate that the large-scale TiO₂ nanorod arrays grown on the pre-treated glass substrate are well-aligned single crystal and grow along [0 0 1] direction. The average diameter and length of the nanorods are approximately 21 and 400 nm, respectively. The photocatalytic activity of TiO₂ nanorod arrays was investigated by measuring the photodegradation rate of methyl blue aqueous solution under UV irradiation (254 nm). And the results indicate that TiO₂ nanorod arrays exhibit relatively higher photocatalytic activity.     

Effects of the size of nano-copper catalysts and reaction temperature on the morphology of carbon fibers

In this study, carbon fibers with different morphologies, including coiled carbon nanofibers and straight carbon fibers, were obtained by the chemical vapor deposition using a Cu-catalytic pyrolysis of acetylene at 250 °C. The influences of nano-copper catalyst particle size and the reaction temperature on the morphology of carbon fibers were investigated. Under the same reaction condition, coiled carbon nanofibers generally were synthesized using nano-copper catalyst with smaller particles size, and bigger copper particles are apt to produce straight carbon fibers. With decreasing of reaction temperature to 200 °C, straight carbon fibers were obtained, instead of coiled carbon nanofibers at 250 °C. The product was characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD).     

Preparation and characterization of the TiO2 ultrafine particles by detonation method

Utilizing the raw materials of TiOSO₄, NaOH, NH₄NO₃ and RDX, the TiO₂ ultrafine particles were prepared under high pressure and high temperature by detonation method. The structure, composition and size distribution of the TiO₂ ultrafine particles were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated the as-prepared TiO₂ ultrafine particles exhibited spherical-like grains and that the average size of particles was 25 ± 5 nm. After being heated at 700 °C for 1 h, TiO₂ particles have entirely completed the anatase-rutile phase transition, which means that detonation method can effectively enhance the anatase-rutile phase transition by lowering the transition temperature. The size of TiO₂ nanoparticles can be effectively controlled because the as-prepared nanoparticles do not have enough time to grow to large and perfect crystallites during the detonation process.     

Photoactivity of brookite–rutile TiO2 nanocrystalline mixtures obtained by heat treatment of hydrothermally prepared brookite

Pure brookite phase was prepared by hydrothermal synthesis of titanium peroxo-complex in the presence of glycolic acid at 220 °C. The structure of prepared brookite samples was determined by X-ray powder diffraction (XRD) and selected area electron diffraction (SAED). The prepared brookite was studied by in situ high temperature XRD in air. The morphology and microstructure characteristics were also obtained by transmission electron microscopy (TEM). The nitrogen adsorption–desorption was used for determination of surface area (BET) and porosity. The method of UV–vis diffuse reflectance spectroscopy was employed to estimate band-gap energies of prepared brookite. The photocatalytic activity of the prepared titania samples were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV irradiation at 365 nm wavelength. The photocatalytic activity of the prepared sample brookite heated to 800 °C in air was higher than nanocrystalline unheated brookite powder.     

An aqueous sol-gel synthesis of chromium(III) doped mesoporous titanium dioxide for visible light photocatalysis

Nanoparticles of titanium dioxide doped with Cr³⁺ ions have been prepared through an aqueous sol-gel method. The mesoporous nature of both pure and Cr³⁺ doped TiO₂ powders, with specific surface area of 7.4 and 6.6 m² g⁻¹, respectively, is maintained even at calcination temperature of 800 °C. The transformation of TiO₂ from the anatase to rutile phase is suppressed up to 800 °C by Cr³⁺ ion doping. Even though surface area values are decreased, the doped materials show improved photocatalytic activity, which may be due to increased crystallinity of the anatase phase without the formation of rutile. Doped materials have a red-shift in the band gap energy and hence, photoactivity under visible light. The rate of photodegradation of methylene blue dye for both pure and doped TiO₂ under visible light has been monitored in this study. The 0.25 mol% Cr(III) doped photocatalyst, calcined at 800 °C, shows the highest photocatalytic activity under visible light with a rate constant of ∼15.8 × 10⁻³ min⁻¹, which is nearly three times higher than that of commercially available Degussa P25 titania (5.8 × 10⁻³ min⁻¹).