Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

Effect of dopant concentration on photocatalytic activity of TiO2 film doped by Mn non-uniformly

The thin films of TiO2 doped by Mn non-uniformly were prepared by sol-gel method under process control. In our preceding study, we investigated in detail, the effect of doping mode on the photocatalytic activity of TiO2 films showing that Mn non-uniform doping can greatly enhance the activity. In this study we looked at the effect of doping concentration on the photocatalytic activity of the TiO2 films. In this paper, the thin films were characterized by UV-vis spectrophotometer and electrochemical workstation. The activity of the photocatalyst was also evaluated by photocatalytic degradation rate of aqueous methyl orange under UV radiation. The results illustrate that the TiO2 thin film doped by Mn non-uniformly at the optimal dopant concentration (0.7 at %) is of the highest activity, and on the contrary, the activity of those doped uniformly is decreased. As a comparison, in 80 min, the degradation rate of methyl orange is 62 %, 12 % and 34 % for Mn non-uniform doping film (0.7 at %), the uniform doping film (0.7 at %) and pure titanium dioxide film, respectively. We have seen that, for the doping and the pure TiO2 films, the stronger signals of open circuit potential and transient photocurrent, the better photocatalytic activity. We also discusse the effect of dopant concentration on the photocatalytic activity of the TiO2 films in terms of effective separation of the photon-generated carriers in the semiconductor. (C) Versita Warsaw and Springer-Verlag Berlin Heidelberg. All rights reserved.

A mechanism for enhanced photocatalytic activity of silver-loaded titanium dioxide

In this paper, silver-loaded TiO2 photocatalyst was prepared by photochemical impregnation method and characterized by transmission electron microscopy (TEM), diffuse reflectance spectra (DRS), photooxidation of phenol and photoreduction of Cr(VI). Electron paramagnetic resonance (EPR) was used to detect photoproduced paramagnetic radicals. The correlation of photocatalytic activity and photogenerated reactive species was discussed, and the mechanism of silver-loaded TiO2 for enhancement of photocatalytic activity was elucidated. The results show that deposited silver on TiO2 Surface acts as a site where electrons accumulate. The better separation between electrons and holes on the modified TiO2 surface allowed more efficiency for the oxidation and reduction reactions. The enhanced photocatalytic activity was mainly attributed to the increased amounts of O-2(.-) reactive species and surface Ti3+ reactive center on silver-loaded TiO2 photocatalyst. (C) 2004 Published by Elsevier B.V.

The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment

In this study, conventional TiO2 powder was heated in hydrogen (H-2) gas at a high temperature as pretreatment. The photoactivity of the treated TiO2 samples was evaluated in the photodegradation of sulfosalicylic acid (SSA) in aqueous suspension. The experimental results demonstrated that the photodegradation rates of SSA were significantly enhanced by using the H-2-treated TiO2 catalysts and an optimum temperature for the H-2 treatment was found to be of 500-600 degreesC. The in situ electron paramagnetic resonance (EPR) signal intensity of oxygen vacancies (OV) and trivalent titanium (Ti3+) associated with the photocatalytic activity was studied. The results proved the presence of OV and Ti3+ in the lattice of the H2-treated TiO2 and indicated that both were contributed to the enhancement of photocatalytic activity. Moreover, the experimental results presented that the EPR signal intensity of OV and Ti3+ in the H-2-treated TiO2 samples after 10 months storage was still significant higher than that in the untreated TiO2 catalyst. The experiment also demonstrated that the significant enhancement occurred in the photodegradation of phenol using the H-2-treated TiO2. (C) 2002 Elsevier Science Ltd. All rights reserved.

Hydrothermal Synthesis and High Photocatalytic Activity of 3D Wurtzite ZnSe Hierarchical Nanostructures

Novel 3D wurtzite ZnSe hierarchical nanostructures have been synthesized by a mild hydrothermal treatment. The as-prepared flowerlike nanostructures efficiently catalyze the photodegradation of methylene blue and ethyl violet present in aqueous solutions under UV light irradiation, exhibiting higher photocatalytic activity than the commercially available photocatalysts P25 and ZnSe microspheres. We also demonstrate that flowerlike morphology is important for the excellent photocatalytic activity.

Preparation of TiO2 nanocrystallites by hydrolyzing with gaseous water and their photocatalytic activity

TiO2 nanocrystallites were prepared front precursors tetra-n-butyl titanate (Ti(OC4H9)(4)) and titanium tetrachloride (TiCl4). The precursors were hydrolyzed by gaseous water in autoclave, and then calcined at predetermined testing temperatures. The samples were characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectra (FT-IR), and UV-vis diffuse reflectance spectra (DRS). The photocatalytic activities of the samples were evaluated by the photobleaching of methylene blue (MB) in aqueous solution and the photocatalytic oxidation of propylene in gas phase at ambient temperature. The results showed that the anatase phase nanocrystalline TiO2 could be obtained at relatively low temperatures (for precursor Ti(OC4H9)4 at I I VC and for TiCl4 at 140 degrees C, respectively), and that the as prepared samples exhibited high photocatalytic activities to photobleach MB in aqueous solution. As the calcination temperatures increasing. the decolor ratio of MB increased and reached the maximum value of nearly 100% at 600 degrees C, and then decreased. The photobleaching of MB by all samples followed the pseudo-first-order kinetics with respect to MB concentration.

Effect of surface state properties of TiO2 nanoparticle film on its photocatalytic activity

TiO2 nanoparticle film catalysts with different thicknesses were prepared by plasma-enhanced chemical vapor deposition(PECVD) method and the surfaces were subsequently treated by TiCl4 or O-2 plasma. Two kinds of TiO2 films with different surface properties were obtained. Their surface microstructures and energy levels of surface states were tested by AFM, XRD, SPS, The photocatalytic activities of the catalysts were determined via photodegradation experiments of phenol. The results demonstrated that photocatalytic activities of samples whose surface was treated by O-2 plasma were greater than those treated by TiCl4 plasma. Moreover, photodegradation ratio of phenol during the first hour catalyzed by 0. 17 mu m thickness TiO2 nanoparticle film was greater than other samples. Especially, the difference of photocatalytic activities of TiO2 nanoparticle films treated by TiCl4 or O-2 plasma was respectively explained by energy band theory.

Photocatalytic degradation of AZO dyes by supported TiO2+UVin aqueous solution

The photocatalytic degradation performance of photocatalysts TiO2 supported on 13-X, Na-Y, 4A zeolites with different loading content was evaluated using the photocatalytic oxidation of dyes direct fast scarlet 4BS and acid red 3B in aqueous medium. The results showed that the best reaction dosage of TiO2-zeolite catalysts is about 2 g/l and the photocatalytic kinetics follows first order for all supported catalysts. The photocatalytic activity order of the three series catalysts is 13X type >Y type >4A type. The physical state of titanium dioxide on the supports is evaluated by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD), BET, and FTIR. (C) 2000 Elsevier Science Ltd. All rights reserved.

Photocatalytic water reduction under visible light on a novel ZnIn2S4 catalyst synthesized by hydrothermal method

A novel ZnIn2S4 catalyst synthesized by hydrothermal method shows high and stable photocatalytic activity for water reduction under visible light illumination.

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Enhancement of field emission properties in La-doped ZnO films prepared by magnetron sputtering

Field emissions (FE) from La-doped zinc oxide (ZnO) films are both experimentally and theoretically investigated. Owing to the La-doped effect, the FE characteristic of ZnO films is remarkably enhanced compared with an undoped sample, and a startling low turn-on electric field of about 0.4 V/mu m (about 2.5 V/mu m for the undoped ZnO films) is obtained at an emission current density of 1 mu A/cm(2) and the stable current density reaches 1 mA/cm(2) at an applied field of about 2.1 V/mu m. A self-consistent theoretical analysis shows that the novel FE enhancement of the La-doped sample may be originated from its smaller work function. Due to the effect of doping with La, the Fermi energy level lifts, electrons which tunnelling from surface barrier are consumedly enhancing, and then leads to a huge change of field emission current. Interestingly, it suggests a new effective method to improve the FE properties of film materials.