TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Synthesis of TiO2 nanoparticles by a combined sol-gel ball milling method and investigation of nanoparticle size effect on their photocatalytic activities

TiO₂ nanoparticles were synthesized by a sol-gel method and the effect of ball milling of dried gel on the particle size has been investigated. The results show that the ball milling has a crucial role in preparation of nanosized TiO₂ powder. Also thermal treatment at different temperatures can control the size of prepared nanoparticles. The photocatalytic activities of TiO₂ nanoparticles with different sizes were studied by photocatalytic degradation of Congo red dye using a homemade photoreactor. The photo degradation of Congo red dye was monitored by UV-Vis absorption measurements. It was found that the nanopowders which were synthesized at 550 °C with average particle size of 55 nm show the maximum photocatalytic activities. These nanopowders which were a mixture of anatase and rutile phases did not show the same photocatalytic effect on Eriochrome black, Bromocresol green, Methyl orange and Rose Bengal dyes.     

Removal of the herbicide Bentazon from contaminated water in the presence of synthesized nanocrystalline TiO2 powders under irradiation of UV-C light

A solution-based processing method has been used to synthesize nanocrystalline TiO₂ powders by controlling the hydrolysis of TiCl₄ in an aqueous solution in both anatase and rutile phases. The primary particle sizes of the powders were in the range of 5-15 nm. To determine the crystal phase composition and size of the prepared photocatalysts, X-ray diffraction (XRD) measurements were used. We also studied the photocatalytic removal of the herbicide, Bentazon, from contaminated water in the presence of synthesized nanocrystalline TiO₂ powders under UV light illumination (30 W). The removal efficiency of Bentazon was 16% when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. We have studied the influence of the basic operational parameters such as the different kinds of TiO₂, amount of TiO₂, irradiation time and initial concentration of Bentazon on the photocatalytic removal efficiency of Bentazon. Our results indicated that 99% removal of the herbicide from the solution containing 15 ppm of Bentazon after selecting desired operational parameters could be achieved in a relatively short time, about 90 min. A kinetic model was successfully established for the prediction of removal of Bentazon by the UV/TiO₂ system with any concentration of the herbicide. In this work, we also compared the photocatalytic activity between the commercial TiO₂ and synthesized nanocrystalline TiO₂ powders. The photocatalytic activities of different photocatalysts were tested using the herbicide solution.     

Hydrothermal synthesis of S-doped TiO2 nanoparticles and their photocatalytic ability for degradation of methyl orange

A simple synthesis route to nanocrystalline S-doped TiO₂ photocatalysts by a hydrothermal method at 180 °C was developed and the photocatalytic activity of the obtained powders for the degradation of methyl orange was studied. The products were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The phase composition (anatase/rutile ratio) and the photocatalytic activity of the final materials were found to be markedly influenced by the amount of the incorporated sulphur. On increasing the S-dopant amount, the anatase/rutile ratio and the photocatalytic activity of the as-prepared powders increased.     

Effects of annealing temperature on the photocatalytic activity of N-doped TiO2 thin films

The effects of annealing temperature on the photocatalytic activity of nitrogen-doped (N-doped) titanium oxide (TiO₂) thin films deposited on soda-lime-silica slide glass by radio frequency (RF) magnetron sputtering have been studied. Glancing incident X-ray diffraction (GIAXRD), Raman spectrum, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectra were utilized to characterize the N-doped TiO₂ thin films with and without annealing treatment. GIAXRD and Raman results show as-deposited N-doped TiO₂ thin films to be nearly amorphous and that the rutile and anatase phases coexisted when the N-doped TiO₂ thin films were annealed at 623 and 823 K for 1 h, respectively. SEM microstructure shows uniformly close packed and nearly round particles with a size of about 10 nm which are on the slide glass surface for TiO₂ thin films annealed at 623 K for 1 h. AFM image shows the lowest surface roughness for the N-doped TiO₂ thin films annealed at 623 K for 1 h. The N-doped TiO₂ thin films annealed at 623 K for 1 h exhibit the best photocatalytic activity, with a rate constant (k_a) of about 0.0034 h⁻¹.     

Continuous supercritical hydrothermal synthesis of controlled size and highly crystalline anatase TiO2 nanoparticles

The production of size-controlled and highly crystalline anatase titanium dioxide (TiO₂) nanoparticles was carried out under supercritical hydrothermal conditions (400 °C and 30 MPa) in a continuous flow apparatus with a residence time of 1.7 s. An industrially useful titanium sulfate (Ti(SO₄)₂) solution was used as the starting solution. KOH was used to change TiO₂ solubility and pH and thereby control the particle size. The apparatus comprised two micromixers operating at high temperature. The first mixer was configured to prepare a supercritical aqueous KOH solution from supercritical water (SC-H₂O) and KOH. The second mixer combined this KOH solution with aqueous Ti(SO₄)₂. In situ pH control and homogeneous nucleation were achieved in the second mixer. This two-step high-temperature micromixing process produced reasonably small and homogeneous particles. The particles were characterized by transmission electron microscopy (TEM) on the basis of morphology, average size, and size distribution, together with the coefficient of variation (CV). Powder X-ray diffraction (XRD) was used to determine the crystal structure and crystalline size. The weight loss of material was found through thermogravimetric (TG) measurement. The crystal structure of the product was assigned to the anatase single phase. The average particle size could be adjusted in the range 13–30 nm while maintaining a CV of 0.5 by changing the KOH concentration. At low pH, the powder XRD results for crystallite size were in good agreement with the average particle size measured by TEM, confirming that the products were single crystals of TiO₂ nanoparticles. When the reactor temperature was increased from 400 to 500 °C, the weight loss decreased from 4.5 to 2.5%, keeping the average particle size and high crystallinity of the TiO₂ particles unchanged.     

Nanocrystalline TiO2 on single walled carbon nanotube arrays: Towards the assembly of organized C/TiO2 nanosystems

Arrays of single walled carbon nanotube bundles organized following different architectures have been coated by a homogeneous deposit of nanocrystalline titania. The nanotubes were grown treating nanosized C powders with atomic H in a purpose-designed chemical vapor deposition (CVD) reactor, the subsequent TiO₂ deposition was performed at 400 °C using the metal-organic CVD (MOCVD) technique and titanium tetraisopropoxide Ti(OⁱPr)₄ as a precursor. X-ray diffraction and Raman spectroscopy evidence the anatase structure of the TiO₂ coatings, formed by grains with an average size of about 55 nm. The structural and compositional characteristics of the TiO₂ deposits are not sensitive to the organization of the nanotube arrays, which maintain their pristine architectures. The adopted synthetic procedure opens a new route for the immobilization of anatase-type TiO₂ nanocrystallites onto geometrically varied structures and for the integration of composite nanotube/TiO₂ systems in effective devices.     

Shock-consolidated TiO2 bulk with pure anatase phases fabricated by explosive compaction using underwater shockwave

Titanium dioxide (TiO₂) bulk with pure anatase phases was fabricated by an explosive compaction technique using an underwater shockwave. Dynamic shock pressure of 6 GPa was used to consolidate anatase TiO₂ powders. Its microstructural, crystalline structural and photocatalytic characteristics were observed and measured by various techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and photocatalytic activity measurement system. It was confirmed that the relative density of anatase TiO₂ compact is about 96% (3.73 g/cm³) of the theoretical density (3.89 g/cm³) and a strong surface bonding between particles is formed by a shock energy. In X-ray diffraction analysis, high purity anatase phases, broadened peaks due to lattice defects and decreased crystallite size were found. For the photocatalytic activities, the anatase TiO₂ compact was quite excellent compared to the commercial sintered TiO₂ bulk.     

Disinfection of spring water and secondary treated municipal wastewater by TiO2 photocatalysis

The photocatalytic disinfection of spring water and secondary treated municipal wastewater by means of UV-A irradiation over TiO₂ suspensions was investigated. Water samples were taken from a spring supplying water to the city of Chania, Western Crete, Greece, while wastewater samples were collected from the outlet of the secondary treatment of Chania municipal wastewater treatment plant. The effect of various operating parameters such as photocatalyst type (rutile, anatase, mixture of anatase and rutile) and concentration (0.5-1 g/L), contact time (up to 60 min) and sample pH (6-8) on the disinfection as assessed in terms of faecal indicator microorganisms (total coliforms and enterococci) inactivation was examined. A commercially available Degussa P25 TiO₂ powder, consisting of 75% anatase and 25% rutile, was found substantially more active than pure anatase or rutile for both groups of bacteria inactivation which increased with increasing contact time and catalyst concentration, whereas small pH changes had little effect on destruction. For both groups of bacteria tested, inactivation followed a first order kinetic expression with the gram positive Enterococcus sp. being considerably more resistant to photocatalytic disinfection than total coliforms.     

Pure and (zinc or iron) doped titania powders prepared by sol-gel and used as photocatalyst

Pure and doped (zinc and iron) nanocrystalline titania powders were prepared by the sol-gel route. Doping tends to change the existing crystalline phases and their degree of crystallinity, but particle size distribution and morphology of the particles are also affected. In the pure titania system, the main crystalline phase is anatase but rutile is also present. The doped (Zn and Fe) titania crystallizes only as anatase. The undoped titania shows a bimodal distribution of particles size: fine (20-40 nm) and coarse (300-500 nm) grains. The doped TiO₂ powder also exhibits a much more uniform particle size distribution, with all grains under 40 nm.The photocatalytic efficiency of suspended powders was tested on the decolouration of Orange II aqueous solutions under visible artificial light irradiation. The maximum decolouration reached by the pure TiO₂ was 81% at a rate of 3.6 × 10⁻³ min⁻¹. Iron doping decreases the photocatalytic activity; the maximum dye degradation was only 43% at a rate of 1.3 × 10⁻³ min⁻¹. On the contrary, the performance of Zn-doped titania was better, having a decolouration rate of 17.7 × 10⁻³ min⁻¹.     

Photoanodic oxidation of small organic molecules at nanostructured TiO2 anatase and rutile film electrodes

A number of applications of titanium dioxide including air and water cleaning rely on photocatalytic activity of its anatase form while others making use of UV-shielding and reflectivity properties employ rather the rutile form. Here we compare photoelectrochemical activity of TiO₂ films formed from nanocrystalline anatase and rutile particles of similar sizes and shapes. Particularly high incident photon-to-current conversion efficiencies observed for the oxidation of organic molecules at the anatase films contrast with the poor activity of the nanostructured rutile films.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Plasma dynamic synthesis of highly defective fine titanium dioxide with tunable phase composition

Titanium dioxide is currently one of the most known promising photocatalysts. However, its use in the visible light range is limited due to its high energy gap. In this work, to solve the mentioned problem, it is proposed to obtain highly defect structures of titanium dioxide by means of a high-energy plasma dynamic synthesis method. It possible to synthesize TiO₂ Titanium dioxide powders with a tunable ratio of rutile and anatase modifications, as well as a particle size distribution were synthesized, by optimizing the synthesis conditions, including the process energy and parameters of the gaseous medium. The formation of shock-wave structures in the pulsed synthesis process results in obtaining fine particles of rutile and anatase with a highly defective crystal structure. The final product was revealed to have an extended working absorption spectrum region and a reduced band gap (2.74 eV). A possibility of photocatalytic applications for the synthesized TiO₂ powder was demonstrated in measurements of photocurrent density with time (j-t) under intermittent visible light irradiation.     

Chemical vapor deposition of carbon on particulate TiO2 from CH4 and subsequent carbothermal reduction for the synthesis of nanocrystalline TiC powders

The present study aims to investigate chemical vapor deposition of carbon from CH₄ on TiO₂ particles and to establish optimal conditions for the synthesis of nanocrystalline TiC powders. Mass measurements, XRD, HR-TEM and SEM were used to characterize the products at various stages of the reactions. Oxide particles gained mass rapidly at 1300 K under CH₄ atmosphere and were coated with thin pyrolytic carbon layers of 10-20 nm. XRD analysis showed that the coated powders consisted of C, TiO₂ and titanium sub-oxides. The powders containing ∼33 ± 2 wt% carbon were used for the carbothermal reduction of TiO₂ to TiC at 1600-1800 K under Ar flow. Lattice constant and mass loss of the samples increased to the levels of TiC with temperature and time. Nearly pure TiC powders with a mean particle size of ∼125 nm were synthesized at 1750-1800 K within 30 min.     

Mechanochemical synthesis of MgTa2O6 ceramic

MgTa₂O₆ powders were prepared by mechanochemical synthesis from MgO and Ta₂O₅ in a planetary ball mill in air atmosphere using steel vial and steel balls. High-energy ball milling gave nearly single-phase MgTa₂O₆ after 8 h of milling time. Annealing of high-energy milled powder at various temperatures (700–1200 °C) indicated that high-energy milling speed up the formation and crystallization of MgTa₂O₆ from the amorphous mixture. The powder derived from 8 h of mechanical activation gave a particle size of around 28 nm. Although at low-annealing temperatures the grain size was almost the same as-milled powder, the grain size increased with annealing temperature reaching to around 1–2 μm after annealing at 1200 °C for 8 h.     

Silica-coated nanocrystalline TiO2 with improved thermal stability

Deposition of a SiO₂ coating on anatase TiO₂ nanocrystals is shown to improve their thermal stability. As low as 0.5% Si was shown to preserve the small anatase crystallite size after calcination at 600?°C. Such treatment led to considerable sintering of TiO₂ nanocrystals without the silica with the average particle size growth from 9 to 50?nm, surface area decrease from 135 to 22?m²/g and partial anatase conversion to rutile. The phase composition, crystallite size, and surface area of 5%Si-TiO₂ samples were largely preserved till the temperatures as high as 800?°C whereas the anatase phase was mostly stably even after calcination at 1000?°C. The phase transformation from anatase to rutile in xerogel TiO₂ and TiO₂@SiO₂ samples apparently did not occur until the crystallites grew larger than the critical size about 50?nm. Electron-acceptor sites capable of ionizing perylene to its radical cations were observed on all samples with anatase crystalline structure. So, the silica shell deposition improves the TiO₂ thermal stability without limiting access to the surface active sites.     

Sonosynthesis of nanostructured TiO2 doped with transition metals having variable bandgap

Here is described a sonosynthesis method to produce nanostructured TiO₂ pure and doped (Al, C, Co, Fe and Rh). The synthesized TiO₂ is amorphous and is transformed to anatase, brookite or rutile by heat treatments at temperatures between 100 and 300 °C. Pure TiO₂ can be partially transformed to brookite between 100 and 300 °C. The band gap in all heat treated samples from 100–600 °C is relatively constant, 3.2 eV, except for those doped with Fe. This effect on the band gap is the results of a bi/tri-crystal (anatase:brookite:rutile) framework. Rhodium is the most effective dopant to narrow the band gap, the opposite effect is observed with C. In single phase frameworks the bandgap can be modified ranges from 2.38 to 4.10 eV depending on the dopant. TiO₂ lattices are rigid enough to promote an outwards diffusion of the dopants to the surface of the particles forming nanostructured precipitates. The precipitates develop a network of quantum-dots with sizes between 5 and 10 nm.     

HIPed TiO2 dense pellets with improved photocatalytic performance

The effects of heating method and temperature on physical, structural and photocatalytic behaviors of TiO₂ pellets prepared by conventional heating and hot isostatic pressing have been evaluated. The pellets of submicron TiO₂ powders were heated to 600, 650, 700, 750 and 1000 °C using both processing methods in order to compare anatase to rutile phase transformation and densification behaviors. Bulk densities and porosities were calculated using the Archimedes method. XRD analysis were performed to calculate anatase/rutile ratios. Microstructures were characterized using SEM. Photocatalytic experiments have been performed under full spectrum irradiation. Degraded methylene blue samples were periodically monitored through UV–vis spectrophotometer to determine degradation kinetics. Anatase to rutile transformation is slightly faster and densification is better for lower temperatures for conventional heating, however HIPing gives better densification above 750 °C as it also retards rutile transformation. Mixed phase structures and HIPed samples showed the best photocatalytic performance which makes this method advantageous.     

Sonochemical synthesis of LaMnO3 nano-powder

We report the preparation of LaMnO₃ nanosized powder by the sonochemical process. Sodium dodecyl sulphate (SDS) was used as surfactant, to prevent agglomeration. The particle size obtained in this method was 19–55 nm. The phase formation temperature of LaMnO₃ was 700 °C which is lower than other conventional processes. So sonochemical process is cost effective and it is more acceptable considering its ease of preparation in comparison to other conventional processes. Powder synthesized was characterized by measuring crystallite size, specific surface area, morphology and by thermal analysis. The particle sizes of the powders were controlled by calcinations schedule. Narrow size distribution and core and shell structure of the prepared powder was revealed by transmission electron microscopy.     

Study on the formation process of Al2O3-TiO2 composite powders

Fine particles of anatase were suspended in solutions of ammonium alum with Al₂O₃/TiO₂ molar ratios from 0.1:1 to 7:1. By spray drying the suspensions and calcining the spray-dried powders, Al₂O₃-TiO₂ composite particles were obtained. The results show that after the spray drying, coatings of ammomium alum are formed on the surface of the anatase particles, leading to composite precursor powders (CCPs) with larger particle sizes. Upon calcining the CCPs, ammomium alum pyrolyzes to amorphous Al₂O₃ and anatase transforms into rutile. Both are mainly responsible for the observed particle size reductions as well as the densification of each composite particle. The in-situ formed α-Al₂O₃ and rutile may have higher reactivities, forming aluminum titanate at 1150 °C, about 130 °C lower than the theoretical temperature for the formation of Al₂TiO₅ by solid reaction. The reaction between α-Al₂O₃ and rutile starts from the interface between the anatase and the alum coating and mainly takes place in the single particles formed by spray drying. The molar ratio of Al₂O₃ to TiO₂ influences the final crystalline phases in the composite powders, but not stoichiometrically.