Effect of TiO2 nanotubes with TiCl4 treatment on the photoelectrode of dye-sensitized solar cells

In this study, we used the electrochemical anodization to prepare TiO₂ nanotube arrays and applied them on the photoelectrode of dye-sensitized solar cells. In the field emission scanning electron microscopy analysis, the lengths of TiO₂ nanotube arrays prepared by electrochemical anodization can be obtained with approximately 10 to 30 μm. After titanium tetrachloride (TiCl₄) treatment, the walls of TiO₂ nanotubes were coated with TiO₂ nanoparticles. XRD patterns showed that the oxygen-annealed TiO₂ nanotubes have a better anatase phase. The conversion efficiency with different lengths of TiO₂ nanotube photoelectrodes is 3.21%, 4.35%, and 4.34% with 10, 20, and 30 μm, respectively. After TiCl₄ treatment, the efficiency of TiO₂ nanotube photoelectrode for dye-sensitized solar cell can be improved up to 6.58%. In the analysis of electrochemical impedance spectroscopy, the value of R_k (charge transfer resistance related to recombination of electrons) decreases from 26.1 to 17.4 Ω when TiO₂ nanotubes were treated with TiCl₄. These results indicate that TiO₂ nanotubes treated with TiCl₄ can increase the surface area of TiO₂ nanotubes, resulting in the increase of dye adsorption and have great help for the increase of the conversion efficiency of DSSCs.     

Effects of I and F codoped TiO2 on the photocatalytic degradation of methylene blue

Nanocrystalline I-F-codoped TiO₂ was prepared by a sol-gel-impregnation method, using tetrabutylorthotitanate in a mixed NH₄I-NH₄F aqueous solution. The as-prepared TiO₂ was characterized with UV-vis diffuse reflectance spectra, X-ray diffraction and nitrogen adsorption. The degradation of methylene blue (MB) over as-prepared TiO₂ in aqueous solution under simulated sunlight irradiation was remarkably enhanced by codoping with I and F. The effects of codoping and calcination temperature on the photocatalytic activity and microstructures were investigated. The photocatalytic activity of as-prepared I-F-codoped TiO₂ was remarkably higher than that of pure, I-doped, and F-doped TiO₂ when the molar ratios of I and F to Ti were kept in the value of 10. The influence of I-F-modification on the photocatalytic activity was discussed by considering the higher surface area, entire anatase phase, effective dopant content, and stronger absorbance of sunlight, corresponding to the higher quantum efficiency. In addition to a complete removal of color, the as-prepared TiO₂ was simultaneously able to oxidize MB and small amounts of intermediates such as formic acid and phenol were detected. After prolonged sunlight irradiation some intermediates almost vanished, and MB appeared to be eventually mineralized to NH₄⁺, NO₃⁻ and SO₄²⁻.     

Preparation of Unique TiO2 Nano-particle Photocatalysts by a Multi-gelation Method for Control of the Physicochemical Parameters and Reactivity

A novel multi-gelation method to prepare TiO₂ nano-particle photocatalysts showed good performance in controlling the important parameters determining the photocatalytic reactivity, i.e., the particle size, surface area, crystallinity, pore-volume, pore-diameter as well as the anatase and rutile phase composition of the catalysts. In particular, this method at higher pH swing times could prevent the phase transition from anatase to rutile, leading to higher photocatalytic activity. By adopting variations in the pH swing, the TiO₂ nano-particle photocatalysts showed significantly higher photocatalytic reactivity for the complete oxidation of 2-propanol diluted with water into CO₂ and H₂O. It can be considered a viable alternative method for the preparation of high performance TiO₂ nano-particle photocatalysts for widespread commercial applications.     

Preparation of Highly Active TiO2 Nano-particle Photocatalysts by a Flame Aerosol Method for the Complete Oxidation of 2-Propanol

A flame aerosol method has been employed to prepare spherical TiO₂ nano-particle photocatalysts with controlled anatase/rutile phase ratios without calcination at higher temperatures. This method was found to have important advantages since the main factors in achieving high photocatalytic activity such as the particle size, crystallinity and the anatase/rutile phase ratios could be easily controlled. In particular, the incorporation of small amounts of bimetals, such as Fe and Zn, were found to initiate the formation of well-crystalline, small and uniform spherical nano-size particles with a well-defined anatase/rutile phase ratio of around 60/40, similar to P-25 TiO₂. This suppressed the recombination of the photoformed charge carriers leading to a significant increase in the photocatalytic reactivity of the TiO₂ nano-particles. The incorporation of very small amounts of mono-metals, such as Fe, Cr and Zn (around 1 at.%), within the TiO₂ nano-particles led to a slight increase in the photocatalytic activity of the TiO₂ nano-particle photocatalysts for the complete oxidation of 2-propanol dissolved in water into CO₂ and H₂O as compared with the unincorporated pure TiO₂. The incorporation of bimetals of Fe and Zn within TiO₂ (Fe/Zn–TiO₂) nano-particles, on the other hand, led to a remarkable enhancement in the photocatalytic activity as compared with the unincorporated and mono-metal incorporated TiO₂.     

Photocatalysis of methylene blue on titanium dioxide nanoparticles synthesized by modified sol-hydrothermal process of TiCl4

Titanium dioxide nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄, an economic titanium precursor, in a mixed solvent of iso-propyl alcohol and water. As-prepared powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM). To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic activity of TiO₂ powders prepared by the hydrolysis of TiCl₄ in the mixed solutions of iso-PrOH/H₂O exceeded that of commercial TiO₂ powders. The apparent first order rate constants (k _app) for the photodegradation of methylene blue (MB) showed a good correlation with the absorbance area obtained by UV-VIS DRS on wavelength in the limits of used lamp emission 300∼420 nm.     

Preparation and characterization of SO42-/TiO2 and S2O82-/TiO2 catalysts

Nanosized solid superacids SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂, as well as MCM-41-supported SO₄ ²⁻/ZrO₂, were prepared. Their structures, acidities, and catalytic activities were investigated and compared using XRD, N₂ adsorption-desorption, and in situ FTIR-pyridine adsorption, as well as an evaluation reaction with pseudoionone cyclization. The results showed that SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ possess not only nanosized particles with diameters < 7.0 nm, a BET surface greater than 140 cm²/g and relatively regular mesostructures with pores around 4.0 nm, but also a pure anatase phase and strong acidity. Different from the Lewis acid nature of SO₄ ²⁻/ZrO₂/MCM-41, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibit mainly Bronsted acidities. The strongest Bronsted acid sites were produced on SO₄ ²⁻/TiO₂ promoted with H₂SO₄, while Lewis acid sites on S₂O₈ ²⁻/TiO₂ even stronger than those on SO₄ ²⁻/ZrO₂/MCM-41 were generated when persulfate solution was used as sulfating agent. Because of their distinct acid natures, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO₄ ²⁻/ZrO₂/MCM-41. It can be concluded that the existence of more Br?nsted acid sites was favorable for proton participation in the cyclization reaction. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(2): 239–244 [译自: 高校化学工程学报]     

Novel Floating TiO2 Photocatalysts for Polluted Water Decontamination Based on Polyurethane Composite Foam

This paper describes the fabrication of new floating photocatalysts based on composites of low-density polyurethane foams through simple in situ polymerization. Different amounts of TiO₂ were immobilized on polyurethane foams after pre-immobilization of TiO₂ onto organic montmorillonite. The coexistence of TiO₂ and montmorillonite on the polyurethane foams was confirmed by X-ray diffraction, scanning electron microscopy, and Fourier Transform Infrared Analysis. Photocatalytic efficiencies were evaluated from the degradation of Bisphenol A. More than 83% of the initial Bisphenol A was degraded in 2 h which was better than the reference photocatalysis by photocatalyst prepared by direct embedding. The degradation kinetics of Bisphenol A follow the apparent-first-order kinetics with the apparent degradation rate constant (k_ap) increases dramatically from 0.0063 min^?1 to 0.0141 min^?1 as TiO₂ loading increases from 10wt% to 40wt%. The density of all the prepared catalysts varied from 0.31 g cm^?3 to 0.62 g cm^?3, indicating the photocatalysts possess excellent floating properties which help directly utilize radiation in photocatalysis without any energy loss incurred in transmitting through water. To conclude, the results demonstrate that the prepared material could be an efficient alternative material for future efforts in wastewater treatment.     

TiO2/ZnO Supported on Sepiolite: Preparation,Structural Characterization,and Photocatalytic Degradation of Flumequine Antibiotic in Aqueous Solution

In this study, TiO₂, ZnO, TiO₂/ZnO (Ti/Zn), and TiO₂/ZnO/Sep (Ti/Zn/Sep) catalysts have been synthesized using sol–gel and chemical precipitation method. Their photocatalytic performances have been compared using Flumequine (FLQ) antibiotic. X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), N₂-adsorption, and the determination of a zero point charge has been used to characterize the synthesized catalysts. The degradation studies showed that the catalytic efficiency of Ti/Zn/Sep is higher than that for other catalysts. The operational parameters such as pH, initial FLQ concentration, and catalyst dosage were evaluated. UV–vis and high-resolution mass spectroscopy (HRMS) analyses were used to determine the degradation efficiency and products. ZnO played a major role in the FLQ degradation process, and sepiolite contributed to adsorption of FLQ on the catalyst surface enormously. The catalysts exhibited 11%, 23%, 63%, and 85% degradation efficiency for ZnO, TiO₂, Ti/Zn, and Ti/Zn/Sep in the decomposition of FLQ, respectively.     

Photocatalytic activity of porous titania nanocrystals prepared by nanoscale permeation process in supercritical CO2: Effects of supercritical conditions

Porous TiO₂ nanocrystals (PTN) were synthesized using activated carbon templates with supercritical CO₂ by using the nanoscale permeation (NP) process. The photoactivity of PTN was tested by methylene blue (MB) degradation. Compared with the commercially available P-25, all PTN exhibited significant photocatalytic degradation of MB mainly due to their porous structure with high surface area, high hydroxy concentration and small crystalline size. The optimum temperature and pressure are found to be 60 °C and 26 MPa, under which obtained PTN-1 shows the highest photoactivity and slow deactivation for MB degradation after 15 trials.     

Preparation, Characterization and Photocatalytic Activities of F-doped TiO2 Nanotubes

F-doped TiO₂ nanotubes were prepared by impregnation method. The prepared catalysts were characterized by XRD, TEM, and XPS. The photocatalytic activity of F-doped TiO₂ nanotubes was evaluated through the photodegradation of aqueous methyl orange. The experiments demonstrated that the F-doped TiO₂ nanotubes calcined at 300 °C possessed the best photocatalytic activity. Compared with pure TiO₂ nanotubes, the doping with F⁻ significantly enhanced the photocatalytic efficiency. The high photocatalytic activity was ascribed to several beneficial effects produced by F-doping: creation of oxygen vacancies, presence of Ti³⁺, and so on. An erratum to this article can be found at     

On the effects of the sol-gel synthesis parameters on textural and structural characteristics of TiO2

The effects of alcohol/alkoxide, water/alkoxide molar ratios, acid addition, type of solvent, reaction temperature and calcination temperature on textural, structural and morphological characteristics of TiO₂ were studied. The results show that surface area, pore size distribution and crystalline phases were very sensitive to preparation conditions.     

Preparation and Characterization of Multi-functional Titanium Dioxide Photocatalysts

Recent research trends of the preparation and characterization of highly efficient titanium oxide-based photocatalysts modified by different methods are reviewed on the basis of studies done in our laboratory. Special attention is focused on the preparation and characterization of TiO₂ photocatalysts prepared by the transitional metal doping and noble metal deposition method, especially combining above two methods. Fe³⁺ doped together with Au deposited TiO₂ (Au/Fe³⁺–TiO₂) was successfully prepared, which shows excellent photocatalytic activity for degradation of methyl orange (MO) under both UV and visible light (λ > 420 nm) illumination. Fe³⁺ has been confirmed by EPR to substitute for Ti⁴⁺ in the TiO₂ lattice, and Au exists as Au⁰ on the surface of the photocatalyst indicated by the results of XRD. Fe³⁺ and Au have synergistic effects on improving the photocatalytic activity of TiO₂. A proposed mechanism concerning the synergistic effects is discussed to explain the improvement of the photocatalytic activities.     

Photocatalytic Properties of Silica-supported TiO2

TiO₂ supported on SiO₂ surface is effective on the recovery of photocatalyst, morphological control, and coating on the substrate. Furthermore, it shows much higher photocatalytic activity than pure TiO₂. The silica support is quite influential on the surface properties of TiO₂ supported on SiO₂. The enhanced photocatalytic activity of TiO₂–SiO₂ could be explained by the effects of surface area, adsorption, band-gap energy and local structure. However, it is difficult to say which one is the most important factor responsible for the photocatalytic property of TiO₂–SiO₂. For example, the reduction of particle size could effect on both of the surface area and band-gap energy. And, Ti–O–Si bonds could modify the band-gap energy and local structure. Therefore, the photocatalytic properties of TiO₂–SiO₂ should be expressed by sum of many factors such as surface area, adsorption, band-gap energy and local structure.     

Photocatalytic microreactor study using TiO2-coated porous ceramics

Two kinds of porous ceramic disks, having through-holes with diameters of 0.1 and 0.05 mm, were coated with TiO₂ using two different starting solutions: titanyl(IV)acetylacetonate and a commercial titania sol (STS-01). The morphology of these porous ceramics before and after TiO₂ coating was observed by SEM. The TiO₂-coated porous ceramics were examined as honeycomb photocatalytic microreactors. The photocatalytic activity was evaluated using the decomposition of methylene blue solution for radiation angles of 0° and 10° with respect to the pore axis. The highest photocatalytic activity was obtained for the porous ceramic having the pore diameter of 0.1 mm, coated with titanyl(IV)acetylacetonate and irradiated with a light angle of 0° with respect to the pore axis.     

Photoassisted mineralization of remazole red F3B over NiO/TiO2 and CdO/TiO2 nanoparticles under simulated sunlight

In this work, a series of titania-supported NiO and CdO materials were synthesized by a modified sol-gel process. The prepared photocatalysts were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), and transmission electron microscopy (TEM). The activities of titania-supported NiO and CdO photocatalysts for photocatalytic degradation of Remazole Red F3B (RR) dye, under simulated sunlight, were investigated. The photocatalytic mineralization of an RR dye solution over various NiO-x/TiO₂ and CdO-x/TiO₂ photocatalysts under simulated sunlight was investigated. It was worthy noticing that the photocatalytic activity of titania improved using the prepared catalysts. The prepared TiO₂, NiO-5/TiO₂, and CdO-2/TiO₂ photocatalysts exhibited higher photocatalytic activity under simulated sunlight than did commercial TiO₂. The prepared photocatalysts were stable after photocatalytic degradation of the dye. The observed photocatalytic mineralization of the dye was 51 and 71% over NiO-10/TiO₂ and CdO-2/TiO₂ after 180 min of irradiation, respectively. Juxtaposing a p-NiO-5/TiO₂ semiconductor provided a potential approach for decreasing charge recombination. The prepared photocatalystsNiO-5/TiO₂ and CdO-2/TiO₂ are promising composites for the solar detoxification of textile wastewater.     

Effect of PAA-g-MPEO Comb Polymer on TiO2 Suspensions

A comb PAA-g-MPEO was prepared. The PAA-g-MPEO underwent two thermal degradation steps. First, the decarboxylation and the dehydration of the carboxyl in the PAA backbone took place in the range of 204–313°C; the weight loss in the range of 313–450°C was from decomposition of MPEO chains and the survivor of the decomposed PAA backbone. By adding comb PAA-g-MPEO as disperser to TiO₂ suspensions, TiO₂/PAA-g-MPEO suspensions were prepared. The PAA-g-MPEO was adsorbed onto the surfaces of the TiO₂ particles, and the zeta potential of TiO₂/PAA-g-MPEO suspensions was higher than that of TiO₂ suspensions. Compared with that of TiO₂ suspensions, the viscosity of TiO₂/PAA-g-MPEO suspensions decreased, and the viscosity further decreased with increasing PAA-g-MPEO content. After adding PAA-g-MPEO, the size distribution of the TiO₂ particles in the suspensions became narrow and the average diameter of the TiO₂ particles decreased due to electrostatic repulsions and the steric hindrances of the PAA-g-MPEO.     

Preparation, Characterization and Photocatalytic Activity of TiO2 Formed from a Mesoporous Precursor

A mesoporous TiO₂ precursor has been prepared by the hydrothermal condensation of tetrabutyltitanate in presence of an alkylamine template by three different methods. The surfactants were removed from as-synthesized TiO₂ by calcination and solvent extraction methods. A potential photocatalyst, predominantly present as an anatase phase, was produced in the latter case. The samples were characterized by XRD, FT-IR, low-temperature N₂ adsorption-desorption measurement and solid state UV-visible diffuse reflectance spectroscopy. The photocatalytic activities of all TiO₂ samples were compared using the degradation of phenol as a probe reaction.     

Photocatalytic decomposition of acetic acid on TiO2

During room‐temperature transient experiments, acetic acid decomposes photocatalytically on TiO₂ in an inert atmosphere by two parallel pathways. One pathway forms CO₂ and C₂H₆ in a 2:1 ratio, and H₂O forms with lattice oxygen that was extracted from the surface. The other pathway forms CO₂ and CH₄ in a 1:1 ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

Photoelectric catalytic degradation of methylene blue by C60-modified TiO2 nanotube array

Fullerene (C₆₀)-modified TiO₂ nanotube array (TNA) was prepared by the electrophoresis deposition technique. The as-prepared samples showed the high efficiency for the photoelectric catalytic (PEC) degradation of nonbiodegradable azodyes methylene blue (MB). The highest PEC activity of C₆₀-modified TNA (TNA/C₆₀) was achieved at a lower bias potential (4.0 V), which was 2.3 times of the highest activity of TNA at 5.0 V. The high PEC activity came from the synergetic effect between C₆₀ and TiO₂, which promoted the charge separation, influenced the charge distribution of the electrical double layer and reduced the impedances of the Helemholtz and depletion layers. Moreover, the oxidation of MB was a quick process during the PEC degradation, and the process began with the oxidation of the dimethylamino group, which was different from the photocatalytic (PC) process began with the oxidation of S atom; MB was mineralized completely during PEC degradation.     

Effect of γ-ray Irradiation on the Wettability of TiO2 Single Crystals

The contact angles of the water droplets on TiO₂ single crystal surfaces decreased and became superhydrophilic state by γ-ray irradiation. It was found that these behaviors were dependent on γ-ray irradiation atmosphere, i.e., in air and in N₂ atmosphere (r. h.; 30%) as well as crystal faces of TiO₂ single crystals, i.e., TiO₂ (100) and (110) surfaces. It was also found from the results of UV–Vis and ESR measurements that γ-ray irradiation under N₂ atmosphere led to the oxygen vacancies and associated Ti³⁺, regardless of the presence of gaseous water. Moreover, it was suggested that the organic molecules adsorbed on TiO₂ single crystal surfaces decomposed by γ-ray irradiation.