Photocatalytic activity and OH radical formation on TiO2 in the relation to crystallinity

Two types of TiO₂ samples, ST-01 (Ishihara-Sangyo, Japan) and A11 precursor (Police, Poland), were heat-treated at 400–1000 °C and characterized by the phase composition, crystallite size and lattice strain. These TiO₂ samples were tested for methylene blue (MB) decomposition and OH radical formation. Through heating TiO₂ up to 700 °C for 1 h the single anatase phase was remained, which had improved crystallinity, large crystallite size and very small lattice strain. By extending the calcination time up to 2–5 h, the anatase phase partially transformed to rutile phase, much faster by A11 precursor than by ST-01. Transformation of anatase phase to rutile reduced the rate of methylene blue decomposition, although OH radical formation was the highest in the samples having around 9 mass% of rutile. However, methylene blue decomposition not only depended on OH radical formation on TiO₂ particles, but also the content of even small amount of rutile in TiO₂ reduces markedly the rate of methylene blue decomposition.     

Preparation and characterization of TiO2–SiO2 nano-composite thin films

TiO₂ nanocrystalline particles dispersed in SiO₂ have been prepared by the sol-gel method using titanium- and silicon-alkoxides as precursors. Nano-composite thin films were formed on the glass substrates by dip-coating technique and heat treated at temperatures up to 500 °C for 1 h. The size of the TiO₂ nanocrystalline particles in the TiO₂–SiO₂ solution ranged from 5 to 8 nm. The crystalline structure of TiO₂ powders was identified as the anatase phase. As the content of SiO₂ increased, the anatase phase tended to be stabilized to higher temperature. TEM results revealed the presence of spherical TiO₂ particles dispersed in a disk-shaped glassy matrix. Photocatalytic activity of the TiO₂–SiO₂ (1:1) thin films showed decomposition of 95% of methylene blue solution in 2 h and a contact angle of 10°. The photocatalytic decomposition of methylene blue increased and the contact angle decreased with the content of TiO₂ phase. TiO₂–SiO₂ with the molar ratio of 1:1 showed a reasonable combination of adhesion, film strength, and the photocatalytic activity.     

Photocatalytic decomposition of methylene blue using nanocrystalline anatase titania prepared by ultrasonic technique

Nanocrystalline particles of pure anatase titania were prepared by sol–gel method at ambient temperature using ultrasonication (Ti-US). The advantages of ultrasonication method are demonstrated as compared to the conventional stirring method of preparation of titania (Ti-S). The physico-chemical properties of the samples were investigated by powder XRD, SEM, TEM, low temperature (77 K) nitrogen sorption, and UV–Vis spectroscopic techniques. More uniform distribution/dispersion of the nanoparticles (SEM), marginally higher surface area, better thermal stability, and phase purity are some of the advantages of preparation of nanocrystalline titania by ultrasonication method. The UV–Vis diffuse reflectance spectra of the samples prepared by ultrasonication method were blue shifted compared to pure anatase due to decrease in particle size. The behavior of anatase titania in photocatalytic decomposition of methylene blue in aqueous medium was studied as a function of the method of preparation and the crystallite size. The nanoparticles prepared by ultrasonication method were more effective than both, the sample prepared by conventional stirring method and commercial Degussa P-25. The higher photocatalytic activity of Ti-US is attributed to the more uniform size of the particles as compared to Ti-S samples.     

Carbon-coated anatase: the role of the carbon layer for photocatalytic performance

Carbon-coated anatase-type TiO₂ was prepared by the heat treatment of powder mixtures of photocatalyst TiO₂ (ST-01) with different carbon precursors, poly(vinyl alcohol), hydroxyl propyl cellulose and poly(ethylene terephthalate), at a temperature between 700 and 900 °C for 1 h in an Ar gas flow. Since the carbon layers formed on the TiO₂ particles were porous, the samples prepared showed a high adsorptivity, in addition to the photoactivity of TiO₂. The carbon coating was shown to suppress the phase transition from photoactive anatase to much less active rutile, but seemed to reduce the amount of UV radiation reaching the surface of the TiO₂ particles. A balance among different factors controlled by the carbon layer on the TiO₂ particles was required to get high photocatalytic performance, i.e., high rate constant for the photodecomposition of methylene blue. On the sample prepared at 850 °C with a carbon content of about 3.5 wt%, the highest rate constant in the present work was obtained, in which the transition from anatase to rutile was suppressed and carbon layer was thin enough to transmit UV rays.     

Formation of the Ti4O7 phase through interaction between coated carbon and TiO2

Fine particles ofphotocatalytic anatase TiO₂ prepared through hydrolysis of titanium tetraisopropoxide were coated by carbon. A reduced phase, Ti₄O₇, was formed through interaction between TiO₂ and the coating carbon. EXAFS analysis on this Ti₄O₇ phase showed an intermediate Ti-Ti distance between those in anatase and rutile, which agreed with the structure composed of two-dimensional slabs of Ti-O octahedra separated by a shear plane. This carbon-coated Ti₄O₇ was confirmed to have photocatalytic activity, even though a little lower than anatase, examining the decomposition of methylene blue in water under LTV irradiation.     

EFFECT OF SIZE AND SHAPE OF TITANIUM OXIDE CRYSTALS ON SPECTROPHOTOMETRIC PROPERTIES OF TITANIUM-BEARING PORCELAIN ENAMELS*

Color changes of three titanium enamels given varied firing treatment were investigated. The size and shape of titanium oxide particles were studied with the electron microscope, the relative amounts of anatase and rutile were determined from X-ray analyses, and spectrophotometric curves of the fired panels were made. Electron micrographs showed that rutile particles recrystallized as needles or “sticks,” whereas anatase appeared as ill-defined, irregularly shaped, rounded particles. With increasing firing temperature or firing time (1) rutile particles showed a greater increase in size than anatase particles, (2) the amount (by weight or volume) of anatase crystals decreased and the amount of rutile crystals increased, and (3) a color change from blue-white to cream-white was observed. The change in color seemed to be related to the scattering of blue light by small particles at lower temperatures or shorter periods of firing. As the size of opacifying particles increased, the scattering of blue light decreased, and the characteristic absorption of visible light in the shorter wave lengths was more apparent. In enamels containing both anatase and rutile, the smaller anatase crystals were predominant at lower and the larger rutile crystals at higher temperatures, so that sharp changes of color were observed as the firing temperature was increased.     

Phase Formation and Microstructure of Titanium Oxides and Composites Produced by Thermal Plasma Oxidation of Titanium Carbide

The phase formation and microstructure of titanium oxides and composites produced by Ar–O₂ thermal plasma oxidation of titanium carbide powders were investigated in detail by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Relationships between the phase compositions and microstructures of the oxides were established by combined structural and phase analyses, in correlation with synthesis conditions and phase formation mechanisms. It is revealed that vapor condensation favored the formation of anatase, which existed as smaller particles, while liquid/solid oxidation favored the formation of rutile, which appeared as larger particles or composites. A higher oxygen input in the plasma gases (Ar + O₂) enhanced the formation of anatase due to impeded oxidation and evaporation. A small amount of Ti₄O₇ and Ti₃O₅ was detected in the larger particles coexisting with rutile or TiC. These suboxides were formed as intermediates in solid oxidation of TiC or precipitated from the Ti–C–O melt during cooling. Furthermore, extensive cracks, dislocations and stresses were observed in the monolithic rutile and composites, in association with the rapid quenching in this high-temperature in-flight oxidation process.     

Flame synthesis of titania particles from titanium tetraisopropoxide in premixed flames

An experimental investigation of flame synthesis of titania particles was conducted in premixed flames. The titanium precursor and silicon dopant used in this study were titanium tetraisopropoxide (TTIP) and hexamethyldisiloxane (HMDS), respectively. The objective of this study was to investigate the influence of flame condition, TTIP concentration, and HMDS on the phase composition and particle morphology of titania synthesized in flames. It was found that the anatase content of titania particles made in flames was appreciably increased by the increase of oxygen concentration in the oxidizer. The increase of flame temperature results in the decrease of anatase content. A significant increase in rutile content of titania particles was observed by increasing the particle residence time at high temperatures. The doping of HMDS in flames inhibits the transformation of anatase to rutile phase and, therefore, reduces the rutile content of product particles. Under the flame doped with low concentrations of HMDS, titania particles with SiO₂ particle agglomerates attached were produced. Further increase of the HMDS concentration up to the Si to Ti molar ratio equal to 0.375 results in the formation of a large amount of SiO₂ agglomerates in the product.     

Influence of temperature schedules on particle size and crystallinity of titania synthesized by vapor-phase oxidation route

Crystalline TiO₂ particles were produced in a tubular flow reactor by chemical vapor synthesis using titanium tetrachloride as a starting material in oxygen containing atmospheres. The dependence of particle size, morphology and crystalline phase of titania on temperature schedules including the reactor temperature, the oxygen preheated temperature and the product cooling measure were explored. It is found that there are two opposite effects of temperature on particle size and crystalline phase content. The particle size distribution, SEM and TEM of resulting powders show that the grain size is controlled by the relative magnitudes of the nucleation rate and growth rate, both of them being subject to the temperature schedules. XRD indicates that particles crystalline phase is predominately anatase and the rutile content increment is not consistent with temperature increase. Anatase titania can be converted to rutile by addition of crystal modifier AlCl₃. The element analysis by EDS shows that Al enriches on the particle outer surface.     

Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Chemical and kinetic features of oxidation of powder titanium carbide

Methods of complex thermal and x-ray phase analysis combined with thermodynamic computations are used to study the mechanism of high-temperature oxidation of TiC. It is shown that oxidation under the conditions of programmed heating occurs in three stages. In the first stage, anatase is formed on the surface of the particles. In the second stage, the chemical reaction of the formation of anatase occurs against the background of an anatase → rutile phase transformation. The third stage is characterized by the formation of a rutile layer. The particles of rutile formed as a result of the phase transformation serve as nuclei for the growth of the new phase.     

Flame aerosol synthesis and characterization of pure and carbon coated titania nano powder

Carbon coated titanium dioxide (TiO₂) nano powder has been synthesized by combustion of TiCl₄ precursor in a laminar diffusion flame using inexpensive liquid petroleum gas (LPG) as a fuel, air as an oxidant, nitrogen gas as a carrier, and characterized with regard to phase(s), surface area, carbon content, morphology and optical absorption. The product is shown to contain both the anatase and rutile phases and exhibits (i) decrease in rutile content, (ii) increase in BET specific surface area, and (iii) increase in the amount of carbon (soot) present with increase in fuel flow rate. Further, the maximum attainable temperature depends on carbon content and determines the phase content and morphology of nano powder, e.g. spherical particles result and display reduced agglomeration when carbon content is more. The rutile phase essentially emerges by transformation of the anatase phase, formed initially with lattice parameters somewhat smaller than the bulk due to oxygen deficiency. On the other hand, use of oxygen (instead of air) leads to formation of spherical particles (average diameter ～104 nm) of a pure anatase phase (as transformation to rutile phase is totally suppressed) with lattice parameters, a=3.776(5) Å, c=9.507(5) Å, close to bulk.     

Porous titania microspheres with uniform wall thickness and high photoactivity

Highly porous titania particles were prepared by depositing thin films of titania, using alternating reactions of TiCl₄ and hydrogen peroxide, on poly(styrene-divinylbenzene) (PS-DVB) template particles via atomic layer deposition (ALD) at 77 °C. The composition of the titania films was verified by XPS analysis and the titania films were directly observed by TEM. TGA/DSC was used to study the thermal decomposition of the polymer template. Porous titania particles with uniform wall thicknesses were successfully obtained after the template PS-DVB was removed by oxidation in air at 400 °C for 24 h. Verification of the resulting porous structure of the titania particles was done by cross-sectional SEM and nitrogen adsorption–desorption analysis. Porous titania particles were treated at different temperatures. XRD analysis was used to determine the microstructure and phase transformation of titania at elevated temperatures. The photocatalytic activity of these porous titania particles was studied by methylene blue decomposition under UV light at room temperature and was found to be comparable to that of commercial anatase titania nanoparticles (~20 nm). Depositing Na₂SO₄ on TiO₂ retarded the TiO₂ phase transformation from anatase to rutile during calcination and, thus, greatly increased the photoactivity of the porous titania particles.     

Role of phase content on the photocatalytic performance of TiO2 coatings deposited by suspension plasma spray

In this work, suspension plasma spraying (SPS) with different hydrogen (H₂) flow rates was employed to produce TiO₂ coatings with various phase contents, oxygen contents, and roughnesses. To eliminate the role of the morphology and oxygen content on the photocatalytic activity, all coatings were polished to reach the same roughness followed by heat-treatment at 550 °C in air for 48 h. Then coatings were analyzed by X-ray diffractometer (XRD), confocal laser microscope, scanning electron microscope (SEM), UV–visible spectrometer, Raman microscope, and thermogravimetric analyzer. The XRD data indicated that the percentage of anatase decreased as function of H₂ flow rates, and almost 46% of anatase transformed to rutile during SPS process at the highest H₂ flow rate. Moreover, the photocatalytic performance was evaluated by monitoring the degradation of methylene blue under visible light irradiation, and the results indicated that anatase phase positively enhances the photocatalytic activity of TiO₂ coatings.     

Kinetics of Anatase TiO2 Surface Area Reduction in a Mixture of HCl, H2O, and O2: l, Experimental Study

Changes in the surface area of anatase TiO₂ were investigated at 690 K as a function of the gas composition in mixtures of hydrogen chloride, water vapor, and oxygen. The chlorine content on the catalyst support was not dependent on the annealing time, which indicates that the adsorption equilibrium is reached very quickly. The kinetics of surface area were obtained as a function of partial pressure of HCI (from 0.1 to 40 kPa), water vapor (from 0.05 to 10 kPa), and oxygen (from 0.4 to 20 kPa). A mathematical expression for the rate of surface area loss was obtained which includes the partial pressure of water and the chlorine content at the surface of anatase.     

INFLUENCE OF CALCINATION ON MICROSTRUCTURES AND PHOTOACTIVITIES OF ALKOXIDE-DERIVED TiO2 NANOPARTICLES PREPARED IN W/O MICROEMULSIONS

Ultrafine titania particles were synthesized by hydrolysis of titanium tetraisoproxide (TTIP) in the nanodroplets of water/NP-5/cyclohexane microemulsions. The as-prepared particles were amorphous, transformed into the anatase phase at 450°C, and completely into the rutile phase at 700°C. The amorphous-to-anatase phase transition temperature decreased with increasing water/surfactant molar ratio. With increasing temperature from 500 to 900°C, the crystallite size increased about twice from 11.7 to 24.4 nm, while the size of the secondary particles, agglomerates of the primary panicles, increased by a factor of about 10. The particles grew largely by intra-agglomerate densification below 700°C, whereas they grew by interagglomerate densification above 700°C. The anatase phase formed at 500-600°C showed considerable photoactivity for the degradation of phenol, whereas both the amorphous phase at 300°C and the rutile phase at 700°C were almost inactive for this reaction.     

Behavior of Silver and Palladium Mixtures during Heating

The behavior of mixtures of silver and palladium during heating in both air and an inert atmosphere was studied using X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dilatometry, and scanning electron microscopy (SEM). In situ high-temperature XRD studies on a commercial 20% palladium material with submicrometer-sized particles indicated that an intermetallic phase, most likely Ag₃Pd, formed in air between 300° and 400°C, the same temperature range where a 13% linear expansion was measured by dilatometry. The DSC data indicated an exothermic peak at 340°C, a temperature where the TGA results indicated that the material had picked up only 0.2% oxygen, compared with the maximum of 1.4% at 525°C. No PdO was detected by XRD at 400°C, which suggests that oxygen was being incorporated in the intermetallic. Microstructural examination using SEM indicated that larger particles, with internal pores, had formed after heating in air to 375°C. When the material was heated in argon for 1 h at 400°C, no intermetallic phase or alloy formed, and minimal expansion occurred. When mixtures of larger silver particles (5–30 μm) with palladium particles (1–3 μm) were heated in air, the maximum amount of expansion that occurred increased from 0% for pure palladium up to a maximum of 18% at 75% silver. This result supports the conclusion that expansion is a result of formation of this new phase, in the presence of oxygen, not of the oxidation of the palladium.     

Selective synthesis of TiO2 nanopowders

Nanosized anatase, rutile, brookite, and mixtures of these materials taken in different ratios are synthesized using the detonation method with variations in the densities and ratios of explosives composed of the TiO₂ precursor, NH₄NO₃, and C₃H₆N₃(NO₂)₃. It is shown that the phase composition, the phase content, and the average particle size of TiO₂ nanopowders depend on the composition of the explosive mixtures and their densities. When the weight ratio between the C₃H₆N₃(NO₂)₃ compound and the TiO₂ precursor lies in the range 0.695–1.270, the average size of rutile particles is larger than that of anatase particles by a factor of approximately two.     

Physical Processes Involved in Production of the Ancient Pigment, Egyptian Blue

Egyptian blue, which was the first synthetic pigment to be used in antiquity, consists of crystals of calcium-copper tetrasilicate (i.e. cuprorivaite (CaCuSi₄O₁₀)). The physical processes associated with the formation of Egyptian blue were investigated by high-temperature X-ray diffraction measurements on synthetic mixtures of quartz, malachite, and calcium carbonate. The high-brilliance, high-energy radiation ID15B beamline at the European Synchrotron Radiation Facility was necessary to ensure good time/temperature resolution, penetration, and high-quality data. The results established that the Egyptian blue crystals are formed through nucleation and growth within a liquid or glass phase, even for mixtures with an alkali content as low as 0.3 wt% soda. Furthermore, the microstructures observed in a scanning electron microscope indicated the ancient Egyptian blue pigments were produced from mixtures containing several weight percent of alkali.