A novel approach towards high-performance composite photocatalyst of TiO2 deposited on activated carbon

TiO₂ photocatalysts deposited on activated carbon (TiO₂/AC) were prepared by dip-hydrothermal method at 180 °C using peroxotitanate as a precursor, then calcinated at 300-800 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and the nitrogen absorption. Their photocatalytic activity was evaluated by degradation of methyl orange (MO). The results showed that TiO₂ particles of anatase type were well deposited on the activated carbon surface. TiO₂/AC calcinated at 600 °C exhibited the best photocatalytic performance. For the comparison, the same photocatalysis experiment was carried out for two mixtures of commercial TiO₂ (Degussa P25) with AC and synthetic TiO₂ with AC. It was found that the composite catalyst TiO₂/AC was better than the two mixtures. Besides, different from fine powdered TiO₂, the granular TiO₂/AC photocatalysts could be easily separated from the bulk solution and reused; indeed, its photocatalytic ability was hardly decreased after a five-cycle for MO degradation. The kinetics of the MO degradation fitted well the Langmuir-Hinshelwood model.     

Preparation of titania hollow spheres by catalyst-free hydrothermal method and their high thermal stabilities

TiO₂ hollow spheres have been prepared by hydrothermal method using carbon spheres as hard templates based on template-directed deposition and calcination in order to remove templates. The morphology and structure of samples were systematically characterized by using various techniques, including XRD, zeta analyzer, SEM, TEM, DRS and FTIR. In this approach, the anatase phase was retained for temperatures up to 900 °C. Moreover, negative charged titania is deposited onto the negative charged surface of carbon spheres, which is proved by nanoparticle size analyzer. Therefore, a possible formation mechanism of TiO₂ hollow spheres was proposed. TiO₂ hollow spheres calcined at 550 °C exhibited the superior photocatalytic activity for the degradation of Rhodamine B, 2.9 times greater than that of Degussa P25. Furthermore, thermal stability of TiO₂ hollow spheres was examined. Fortunately, we found that hollow structures could still be visible distinctly after calcining at 900 °C.     

Effects of microwave drying on the microstructure and photocatalytic activity of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with highly photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate as precursor, and then dried in microwave oven. The prepared samples were characterized by XRD, SEM, TEM, HRTEM and N₂ adsorption-desorption measurement. The photocatalytic activity was evaluated by the photocatalytic degradation of acetone in air under UV light irradiation at room temperature. The effects of microwave drying on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. The results show that microwave drying not only promotes the growth of the pores but also greatly reduces the state of agglomeration within the powders. All the microwave-dried TiO₂ powders show higher photocatalytic activity than Degussa P-25 (P25) and the TiO₂ powders dried by conventional method.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.     

Graphene oxide based Pt-TiO2 photocatalyst: ultrasound assisted synthesis, characterization and catalytic efficiency

An ultrasound-assisted method was used for synthesizing nanosized Pt-graphene oxide (GO)-TiO₂ photocatalyst. The Pt-GO-TiO₂ nanoparticles were characterized by diffused reflectance spectroscopy, X-ray diffraction, N₂ BET adsorption-desorption measurements, atomic force microscopy and transmission electron microscopy. The photocatalytic and sonophotocatalytic degradation of a commonly used anionic surfactant, dodecylbenzenesulfonate (DBS), in aqueous solution was carried out using Pt-GO-TiO₂ nanoparticles in order to evaluate the photocatalytic efficiency. For comparison purpose, sonolytic degradation of DBS was carried out. The Pt-GO-TiO₂ catalyst degraded DBS at a higher rate than P-25 (TiO₂), prepared TiO₂ or GO-TiO₂ photocatalysts. The mineralization of DBS was enhanced by a factor of 3 using Pt-GO-TiO₂ compared to the P-25 (TiO₂). In the presence of GO, an enhanced rate of DBS oxidation was observed and, when doped with platinum, mineralization of DBS was further enhanced. The Pt-GO-TiO₂ catalyst also showed a considerable amount of degradation of DBS under visible light irradiation. The initial solution pH had an effect on the rate of photocatalytic oxidation of DBS, whereas no such effect of initial pH was observed in the sonochemical or sonophotocatalytic oxidation of DBS. The intermediate products formed during the degradation of DBS were monitored using electrospray mass spectrometry. The ability of GO to serve as a solid support to anchor platinum particles on GO-TiO₂ is useful in developing new photocatalysts.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with lanthanum and iodine

The novel visible-light-activated La/I/TiO₂ nanocomposition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by X-ray powder diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG-DSC) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of La/I/TiO₂ was evaluated by studying photodegradation of reactive blue 19 as a probe reaction under simulated sunlight irradiation. Photocatalytic experiment results showed that the maximum specific photocatalytic activity of the La/I/TiO₂ photocatalyst appeared when the molar ratio of La/Ti was 2.0 at%, calcined at 350 °C for 2 h, due to the sample with good crystallization, high BET surface area and small crystal size. Under simulated sunlight irradiation, the degradation of reactive blue 19 aqueous solution reached 98.6% in 80 min, which showed La/I/TiO₂ photocatalyst to be much higher photocatalytic activity compared to standard Degussa P25 photocatalyst. The higher visible light activity is due to the codoping of lanthanum and iodine.     

Comparison of photocatalytic performance of anatase TiO2 prepared by low and high temperature route

Anatase TiO₂ was prepared by a facile sol-gel method at low temperature through tailoring the pH of sol-gel without calcination. As a control, anatase TiO₂ was also synthesized by the conventional sol-gel process, in which calcination at 500 °C was required to transform the amorphous oxide into highly crystalline anatase. As-prepared samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL). Their photocatalytic activities were evaluated by degradation of methyl orange under UV light irradiation. On the basis of experiment results, it could be concluded that TiO₂ prepared by low temperature route showed more advantages in small particle size, highly dispersion nature, abundance of surface hydroxyl groups, strong PL signal, and high photocatalytic activity over TiO₂ obtained by the conventional sol-gel process. Furthermore, the reason of the former possessing higher photocatalytic activity was discussed.     

The photocatalytic application and regeneration of anatase thin films with embedded commercial TiO2 particles deposited on glass microrods

Anatase thin films (<200 nm in thickness) embedding Degussa P25 TiO₂ were prepared by sol-gel method. TiO₂-anatase thin films were deposited on a fiberglass substrate and then ground to obtain glass microrods containing the composite films. The film structure was characterized using Raman spectroscopy, atomic absorption and UV-vis spectrophotometry, and atomic force microscopy. The photocatalytic activity of the composite films, calcined at 450 °C, and the regeneration of the activity under the same experimental conditions, were assessed using gas chromatography to study the photodegradation of phenol, an industrial pollutant, in water under 365 nm irradiation. The film with 15.0 wt.% of P25 TiO₂ was found to be more photoactive (54 ppm of degraded phenol at 6 h of illumination) than the other ones.     

Titanium dioxide nanoparticles prepared by laser pyrolysis: Synthesis and photocatalytic properties

TiO₂ nanoparticles were synthesized via the laser pyrolysis of titanium tetrachloride-based gas-phase mixtures. In the obtained nanopowders, a mixture of anatase and rutile phases with mean particle size of about 14 nm was identified. Using the thermal heated laser nanopowders, mechanically stable films were produced by immobilizing titania nanopowders on glass substrates (the doctor blading method followed by compression). The photocatalytic activity of the prepared films was tested by the degradation of 4-chlorophenol in an aqueous solution under UV-illumination. By referring to known commercial samples (Degussa P25) similarly prepared, higher photocatalytic efficiency was found for the laser-prepared samples.     

Photoactive materials prepared by homogeneous hydrolysis with thioacetamide: Part 2—TiO2/ZnO nanocomposites

Photocatalytic active titanium dioxide (TiO₂)/zinc oxide (ZnO) composite was prepared by homogeneous hydrolysis of a mixture of titanium oxo-sulphate and zinc sulphate in aqueous solutions with thioacetamide and subsequent annealing at the temperature of 600 °C. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission microscopy (HRTEM). Nitrogen adsorption-desorption was used for surface area (Brunauer-Emmett-Teller—BET) and porosity determination. The photoactivity of the prepared TiO₂/ZnO samples was assessed by the photocatalytic decomposition of Orange II dye in an aqueous slurry under irradiation of 254 and 365 nm wavelengths. Under the same conditions, the photocatalytic activity of a commercially available photocatalyst (Degussa P25), the pure anatase TiO₂ nanoparticles and cubic ZnO were examined.     

Photocatalytic performance of silver TiO2: Role of electronic energy levels

Nano-sized silver deposits on the surface of Degussa P25 TiO₂ (Ag-DP25) particles act as sites of electron accumulation where the reduction of adsorbed species takes place. Electrons can be transferred from Degussa P25 TiO₂ (DP25) to Ag particles because of the difference in the work functions of the two materials. The efficiency of the electron transfer depends on the size and the distribution of metal deposits. A significant photocatalytic oxidation enhancement by metal deposit will only be observed if the metal deposits play a more dominant role than just increasing the life time of charge carriers. The properties of metal deposits like, loaded amount, oxidation state of the deposit and its size will influence the performance. Further, a decrease in band-gap in DP25 and Ag-DP25 was observed due to the carbide ion substitution for the oxide ion in TiO₂. Such unintentional carbon incorporation is expected mostly in combustion synthesized materials. Silver metal deposits and unintentional incorporation of the carbon shows the beneficial effect by specific mechanism in the photocatalytic degradation of Congo Red (CR).     

TiO2 thick films supported on reticulated macroporous Al2O3 foams and their photoactivity in phenol mineralization

TiO₂ thick films deposited on macroporous reticulated Al₂O₃ foams with pore size of 10 ppi and 15 ppi were prepared using dip coating from slurries of Aeroxide^® P25 nanopowder and precipitated titania. All prepared films have sufficiently good adhesion to the surface of the substrate also in case of strongly cracked films. No measurable release of deposited TiO₂ after repeated photocatalytic cycles was observed. The photocatalytic activity was characterized as the rate of mineralization of aqueous phenol solution under irradiation of UVA light by TOC technique. The best activity was obtained with Aeroxide^® P25 coated Al₂O₃ foam with the pore size of 10 ppi, annealed at 600 °C. The optimal annealing temperature for preparation of films from precipitated titania could be determined at 700 °C. Films prepared by sol-gel deposition technique were considerably thinner compared to coatings made of suspensions and their photocatalytic activity was significantly smaller.     

Preparation of bimetal incorporated TiO2 photocatalytic nano-powders by flame method and their photocatalytic reactivity for the degradation of diluted 2-propanol

Bimetal incorporated TiO₂ photocatalysts (FeZn–TiO₂) prepared by a flame method showed high photocatalytic activity for the degradation of 2-propanol dissolved in water as compared with mono-metal incorporated or unincorporated TiO₂. By using this flame method, parameters such as uniform particle size, crystallinity as well as the anatase and rutile phase ratio (anatase/rutile) could be controlled without calcination of the catalysts at high temperatures, the parameters being important to achieve a high photocatalytic activity. The presence of a small amount of bimetals such as Fe and Zn plays a vital role as a catalyst in the formation of highly crystalline, small and uniform size particles with defined anatase/rutile phase ratio of around 60/40, this being similar to that of P-25 which is well known as a highly active photocatalyst.     

Synthesis, structure and photocatalytic activity of nano TiO2 and nano Ti1-xMxO2-δ (M = Cu, Fe, Pt, Pd, V, W, Ce, Zr)

We have synthesized 5–7 nm size, highly crystalline TiO₂ which absorbs radiation in the visible region of solar spectrum. The material shows higher photocatalytic activity both in UV and visible region of the solar radiation compared to commercial Degussa P25 TiO₂. Transition metal ion substitution for Ti⁴⁺ creates mid-gap states which act as recombination centers for electron-hole induced by photons thus reducing photocatalytic activity. However, Pt, Pd and Cu ion substituted TiO₂ are excellent CO oxidation and NO reduction catalysts at temperatures less than 100° C.     

Photocatalytic behavior of heavy La-doped TiO2 films deposited by pulsed laser deposition using non-sintered target

We have investigated the control of photocatalytic behavior under deposited conditions of non-sintered target of different molar ratios with TiO₂ and La₂O₃ from 1:0 to 1:2 for heavily La doping, and post-annealing temperature from 600 °C to 1000 °C for crystallizing by pulsed laser deposition. We have successfully crystallized heavily La-doped TiO₂ films with post-annealing temperature over 800 °C and with molar ratio of TiO₂:La₂O₃ over 1:1 on a quartz substrate. Heavily La-doped TiO₂ films are observed the decomposition of methylene blue and a water-splitting reaction in photocatalytic behavior under Xe light irradiation. When stoichiometric La-doped TiO₂ (TiO₂:La₂O₃ = 1: 1) is synthesized with heat-treatment at 900 °C, the best results are obtained under photocatalytic behavior and pure La₂Ti₂O₇ crystalline were obtained.     

Role of Cl ions in photooxidation of propylene on TiO2 surface

The effect of Cl⁻ ions on photooxidation of propylene on TiO₂ semiconductor was investigated. Cl⁻/TiO₂ catalysts were prepared by annealing Degussa P25 TiO₂ in the gas flow of N₂ and Cl₂ under 100-400 °C. The photocatalytic oxidation of propylene was carried out in a continuous flow system, with the chromatograph to analyze the products on line. The experimental results showed that the activity of Cl⁻/TiO₂ catalysts increased as heat-treated temperature decreased. The activity of the sample heat-treated at 100 °C was about two times higher than that of pure TiO₂. Moreover, as to TiO₂, the main product of the propylene photocatalytic oxidation was CO₂, but with Cl⁻/TiO₂ catalysts, not only CO₂ but also trace CO was determined. The adsorbed species on TiO₂ surface before and after reaction were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analyses (TG-DTA) coupled to a mass spectrometer (MS). XPS analysis showed that there was Cl⁻ absorbed on the Cl⁻/TiO₂ surface, and the absorption amount of Cl⁻ decreased after the photooxidation reaction of propylene. TG-DTA-MS analysis confirmed chlorine absorbed on the surface of TiO₂ in the form of Cl⁻ ion. These results illuminated that absorbed Cl⁻ on the surface of TiO₂ formed a weak physical absorption on TiO₂ at low temperature, and subsequently participated in the photooxidation of propylene, finally removed from TiO₂ surface.     

Oblique angle deposition of TiO2 thin films prepared by electron-beam evaporation

Optical, structural and photocatalytic properties of TiO₂ thin films obliquely deposited on quartz glass substrate using an electron-beam evaporation method were investigated. The photocatalytic activity of the films was evaluated by photodecomposition of methylene blue. An increase in incident deposition angle increased the porosity and surface roughness of the TiO₂ films. As a result, the photocatalytic activity was enhanced with incident deposition angle up to 60°. However, a further increase in incident deposition angle to 75° reduced the photocatalytic activity due to a lack of the crystalline phase.     

Low-temperature preparation of anatase titania-coated magnetite

A composite photocatalyst with an anatase titania shell and a magnetite core was prepared in a novel way at low temperature (75 °C at most) by coating photoactive titanium dioxide onto a magnetic Fe₃O₄ core. The photocatalytic activity of the prepared photocatalyst was evaluated by the degradation of model contaminated water of phenol and compared to single-phase titania (either Degussa P25 or prepared titania without magnetic Fe₃O₄). The results showed that the photoactivity was slightly depressed. Then, a remarkable improvement in photoactivity was achieved by modifying the photocatalyst with a SiO₂ layer between the Fe₃O₄ core and TiO₂ shell. The repetitive using of the modified photocatalyst was also investigated, and experimental results illustrated that the photocatalytic-degraded ratio of phenol was still higher than 80% after six cycles.     

Low temperature synthesis of iodine-doped TiO2 nanocrystallites with enhanced visible-induced photocatalytic activity

Iodine-doped TiO₂ nanocrystallites (denoted as I-TNCs) were prepared via a newly developed triblock copolymer-mediated sol-gel method at a temperature of 393 K. I-doping, crystallization and the formation of porous structure have been simultaneously achieved. The obtained particles were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-vis spectrophotometer. The results indicated that the as-prepared I-TNCs possessed a diameter of ca. 5 nm with anatase crystalline structure and a specific surface area of over 200 m² g⁻¹. The presence of iodine expanded the photoresponse in visible light range, and led to enrich in surface hydroxyl group on the TiO₂ surface. Compared with the commercial photocatalyst P25, the I-TNCs significantly enhanced the photocatalytic efficiency in the degradation of rhodamine B and 2,4-dichlorophenol, and the I-TNCs with 2.5 mol% doping ratio exhibited the best photocatalytic activity.     

Titania deposited on soft magnetic activated carbon as a magnetically separable photocatalyst with enhanced activity

Magnetically separable composite photocatalysts, TiO₂ deposited on soft magnetic ferrite activated carbon (TFAC), were prepared by sol-gel and dip-coating technique. The prepared composites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectra (FTIR), optical absorption spectroscopy, vibrating sample magnetometer (VSM) and nitrogen adsorption. These photocatalysts exhibited enhanced photocatalytic activity compared to Degussa P25 for the degradation of methyl orange (MO) in aqueous solution. The kinetics of MO degradation was well fitted to the Langmuir-Hinshelwood model. The samples showed good magnetic response and could be completely recovered by an external magnet. Furthermore, the photocatalysts could maintain high photocatalytic activity after five cycles, and the degradation rate of MO was still close to 90%.