Photocatalytic oxidation of 2-propanol under visible light irradiation on TiO<Subscript>2</Subscript> thin films prepared by an RF magnetron sputtering deposition method

Visible light-responsive TiO₂ (Vis-TiO₂) thin films able to absorb UV and visible light in wavelength regions of 250–600 nm were successfully developed by applying a radio-frequency magnetron sputtering deposition method. These Vis-TiO₂ thin films exhibited high activity for the photocatalytic oxidation of 2-propanol diluted in water even under visible light irradiation (λ ≥ 450 nm). The photocatalytic activity of Vis-TiO₂ thin films was dramatically enhanced by the deposition of Pt particles on the surface. Secondary ion mass spectrometry measurements revealed that Pt particles are distributed from the top surface to the deep bulk of Vis-TiO₂ thin films with a columnar structure. The unique columnar structure of Vis-TiO₂ thin films plays an important role in the high photocatalytic performance.     

Separate evolution of H2 and O2 from H2O on visible light-responsive TiO2 thin film photocatalysts prepared by an RF magnetron sputtering method

Visible light-responsive TiO₂ thin film photocatalysts (Vis-TiO₂) have been prepared on Ti metal foil (Vis-TiO₂/Ti) or ITO glass (Vis-TiO₂/ITO) substrates by a radio-frequency magnetron sputtering (RF-MS) method. The UV–Vis spectra as well as photoelectrochemical performance of Vis-TiO₂ were affected by various calcination treatments such as calcination in air or NH₃. Calcination treatment in NH₃ (1.0 × 10⁴ Pa, 673 K) was particularly effective in increasing the visible light absorption of Vis-TiO₂ as well as in enhancing its photoelectrochemical performance and photocatalytic activity. A novel Vis-TiO₂ thin film photocatalyst (Vis-TiO₂/Ti/Pt) was prepared by an RF-MS method where Vis-TiO₂ was deposited on one side of a Ti metal foil substrate and nanoparticles of Pt were deposited on the other side. The separate evolution of H₂ and O₂ from H₂O could be successfully achieved by using an H-type glass cell consisting of two aqueous phases separated by Vis-TiO₂/Ti/Pt and a proton-exchange membrane. It was found that the rate of the separate evolution of H₂ and O₂ was also dramatically enhanced by calcination treatment of Vis-TiO₂ in NH₃.     

Effect of the sputtering parameters on the physical properties and photocatalytic reactivity of TiO2 thin films prepared by an RF magnetron sputtering deposition method

Visible light-responsive TiO₂ (Vis-TiO₂) thin films were successfully developed by applying a radio-frequency magnetron sputtering deposition method by controlling various sputtering parameters such as the substrate temperature, Ar gas pressure, and the target-to-substrate distance. UV–Vis, XRD and SEM investigations revealed that optical property, the crystal structure, and photocatalytic activity of Vis-TiO₂ are strongly affected by the sputtering parameters during the deposition step. Vis-TiO₂ was found to act as an efficient photocatalyst for the H₂ and O₂ evolution from water under visible light irradiation (λ ≥ 420 nm). SIMS investigations have revealed that a slight decrease in the O/Ti ratio of the TiO₂ thin films plays an important role in the modification of the electronic properties of Vis-TiO₂ thin films, enabling them to absorb visible light.     

Effect of Pt loading on the photocatalytic reactivity of titanium oxide thin films prepared by ion engineering techniques

Platinum-loaded titanium oxide thin-film photocatalysts were prepared by using an ionized cluster beam (ICB) deposition method and a RF magnetron sputtering (RF-MS) deposition method as dry processes. From the results of the photocatalytic oxidation of acetaldehyde with O₂ under UV light irradiation, small amounts of Pt loading (less than 10 nm film thickness) were found to dramatically enhance the photocatalytic reactivity. However, when TiO₂ thin films were loaded with relatively larger amounts of Pt (more than 30 nm as the film thickness), the photocatalytic reactivity became lower than for the pure TiO₂ thin films. Moreover, investigations of the ratio of Pt loaded onto the surface of the thin film catalysts by XPS measurements revealed that the small amounts of Pt loaded exist as very small clusters working to efficiently enhance the charge separation, whereas, large amounts of Pt covers the entire surface of the TiO₂ thin films, resulting in a decrease of the photocatalytic reactivity.     

Ion engineering techniques for the preparation of the highly effective TiO<Subscript>2</Subscript> photocatalysts operating under visible light irradiation

The successful application of ion engineering techniques for the development of TiO₂ photocatalysts operating under visible and/or solar light irradiations has been summarized in this review article. First, we have physically doped various transition metal ions within a TiO₂ lattice on an atomic level by using an advanced metal ion implantation method. The metal ion implanted TiO₂ could efficiently work as a photocatalyst under visible light irradiation. Some field tests under solar light irradiation clearly revealed that the Cr or V ions implanted TiO₂ samples showed 2–3 times higher photocatalytic reactivity than the un-implanted TiO₂. Second, we have developed the visible light responsive TiO₂ thin film photocatalyst by a single process using an RF-magnetron sputtering (RF-MS) deposition method. The vis-type TiO₂ thin films showed high photocatalytic reactivity for various reactions such as reduction of NOx, degradation of organic compounds, and splitting of H₂O under visible and/or solar light irradiations.     

Preparation of nitrogen-substituted TiO2 thin film photocatalysts by the radio frequency magnetron sputtering deposition method and their photocatalytic reactivity under visible light irradiation

Nitrogen-substituted TiO2 (N-TiO2) thin film photocatalysts have been prepared by a radio frequency magnetron sputtering (RF-MS) deposition method using a N2/Ar mixture sputtering gas. The effect of the concentration of substituted nitrogen on the characteristics of the N-TiO2 thin films was investigated by UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses. The absorption band of the N-TiO2 thin film was found to shift smoothly to visible light regions up to 550 nm, its extent depending on the concentration of nitrogen substituted within the TiO2 lattice in a range of 2.0-16.5%. The N-TiO2 thin film photocatalyst with a nitrogen concentration of 6.0% exhibited the highest reactivity for the photocatalytic oxidation of 2-propanol diluted in water even under visible (lambda > or = 450 nm) or solar light irradiation. Moreover, N-TiO2 thin film photocatalysts prepared on conducting glass electrodes showed anodic photocurrents attributed to the photooxidation of water under visible light, its extent depending on wavelengths up to 550 nm. The absorbed photon to current conversion efficiencies reached 25.2% and 22.4% under UV (lambda = 360 nm) and visible light (lambda = 420 nm), respectively. UV-vis and photoelectrochemical investigations also confirmed that these thin films remain thermodynamically and mechanically stable even under heat treatment at 673 K. In addition, XPS and XRD studies revealed that a significantly high substitution of the lattice O atoms of the TiO2 with the N atoms plays a crucial role in the band gap narrowing of the TiO2 thin films, enabling them to absorb and operate under visible light irradiation as a highly reactive, effective photocatalyst.     

Photocatalytic property of surface-modified TiO<Subscript>2</Subscript> nanobelts under visible light irradiation

A novel plasmonic photocatalyst, i.e., acid-etched TiO₂ nanobelts attached with Ag/AgI nanoparticles (NPs) was prepared by deposition–precipitation-photoreduction method. Such surface-modified nanobelts had larger area than the normal one. Ag NPs were formed from AgI by photo-reduction under Xenon lamp irradiation. X-ray diffraction, scanning electron microscopy analysis, UV–Vis diffuse reflectance spectra and fluorescence spectra were used to characterize the structure and optical properties of the sample. The obtained sample exhibited strong photodegradation of methyl orange (MO) under visible light irradiation, which were attributed to both the surface plasmon resonance of Ag NPs and the visible light actived AgI. The photodegradation was accomplished by the transfer of photoexcited electrons from the Ag NPs to the acid-etched TiO₂ nanobelts. After four cycles of photodegradation the photocatalyst was still stable. This novel photocatalyst had a high potential application in wastewater-treatment and biomedical engineering.     

Photocatalytic degradation of trichloroethylene on platinum ion-doped TiO<Subscript>2</Subscript> under visible light irradiation

Porous platinum ion-doped TiO₂ (Pt–TiO₂) was prepared by a sol–gel method and demonstrated to have superior photocatalytic activity for the photodegradation of gaseous trichloroethylene (TCE) under visible light (VL) irradiation from a xenon lamp equipped with 422-nm cut-off filter. Kinetic studies were performed to clarify the effect of the doping amounts, space times, VL intensity, and mole fractions of TCE, O₂, and H₂O on the degradation of TCE. Under ultraviolet (UV) irradiation, the photocatalytic activity of Pt–TiO₂ was the same as that of TiO₂, indicating that the doped Pt ion did not act as a recombination center for the photogenerated holes and electrons. Based on the kinetic data and reaction products, we conclude that the photocatalytic degradation of TCE on Pt–TiO₂ under VL irradiation proceeds similarly to TiO₂ under UV irradiation. We also performed the photocatalytic degradation of TCE at the space time of 7.5 × 10⁷ g s mol^?1 in a tubular reactor packed with the Pt–TiO₂ pellets which are more suitable than the Pt–TiO₂ powder for the practical remediation of the contaminated gas. TCE was completely degraded, i.e. 100% conversion was achieved under VL irradiation but only a small quantity of CO₂ was formed with the stoichiometric ratio of [CO₂]_formed/[TCE]_degraded of ca. 0.33. By switching the gas stream containing TCE to humid air, more CO₂ was formed, indicating that the dichloroacetates accumulated on the Pt–TiO₂ surface are photodegradable to CO₂ under VL irradiation.     

Preparation of nano-sized Pt metal particles by photo-assisted deposition (PAD) on transparent Ti-containing mesoporous silica thin film

We have investigated a novel technique for the preparation of nano-sized Pt metals on Ti-containing mesoporous silica (TMS) thin film by photo-assisted deposition (PAD). The transparent TMS thin film was prepared on a quartz plate through sol—gel/spin coating. XRD, UV-Vis and Ti K-edge XAFS measurements revealed the formation of isolated Ti oxide species with a tetrahedral-coordination geometry in the silica framework. Deposition of Pt metal precursor on TMS thin film under UV-light irradiation, followed by reduction with molecular hydrogen, afforded a transparent thin film (Pt/TMS). The formation of highly dispersed nano-sized Pt metals having narrow size distributions was determined by Pd L_III-edge XANES and TEM analysis. The TMS and Pt/TMS thin films have been demonstrated to exhibit a strong hydrophilic property, even before UV irradiation, compared to the common mesoporous silica and TiO₂ thin films. After UV-light irradiation, the contact angle of water droplet on the TMS and Pt/TMS thin films became extremely lower, indicating the appearance of the photo-induced super-hydrophilic property.     

Photocatalytic intercalated material based on HLaNb<Subscript>2</Subscript>O<Subscript>7</Subscript> as host and Cd<Subscript>0.8</Subscript>Zn<Subscript>0.2</Subscript>S as guest

A novel photocatalytic material (Pt,Cd0.8Zn0.2S)/HLaNb2O7 was fabricated by successive intercalation and exchange reactions. The (Pt,Cd0.8Zn0.2S)/HLaNb2O7 possessed a gallery height less than 0.5 nm and showed a broad absorption with wavelength over 370-500 nm. Using (Pt,Cd0.8Zn0.2S)/HLaNb2O7 as catalyst, the photocatalytic H2 evolution was more than 160 cm3·h-1·g-1 in the presence of Na2S as a sacrificial agent under irradiation with wavelength more than 290 nm from a 100-W mercury lamp. Furthermore, the catalyst showed photocatalytic activity even under visible light irradiation.     

In situ synthesis and characterization of TiO<Subscript>2</Subscript> nanoarray films

Based on anodic aluminum oxide (AAO) templates prepared in different acidic solutions, highly ordered aligned titania nanotubes array films have been successfully prepared by the liquid phase deposition method. The effect of AAO template type on the microstructure of titania film have been studied. Using the template with a certain volume fraction of Al₂O₃ (less than 0.71), ordered aligned titania nanotubes were obtained, characterized with an outer diameter of 200 nm and an inner diameter of 100 nm, respectively. However, titania existed as ordered aligned nanorods with the diameter of 100 nm when the template with large volume fraction of Al₂O₃ (larger than 0.71) was used. TiO₂ thin films calcined at 400°C for 4 h have an anatase phase and exhibit good photocatalytic activity, i.e., 75% methylene blue could be degraded under ultraviolet irradiation for 2 h.     

Structural characterization and photocatalytic properties of novel Bi<Subscript>2</Subscript>FeVO<Subscript>7</Subscript>

Bi₂FeVO₇ was prepared by a solid-state reaction technique for the first time and the structural and photocatalytic properties of Bi₂FeVO₇ were studied. The results shows that this compound crystallized in the tetragonal crystal system with space group I4/mmm. Moreover, the band gap of Bi₂FeVO₇ was estimated to be about 2.22(6) eV. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water with Bi₂FeVO₇ as the photocatalyst by ultraviolet light irradiation. Degradation of aqueous methylene blue (MB) dye by photocatalytic way over this compound was further studied under visible light irradiation. Bi₂FeVO₇ shows higher catalytic activity compared to TiO₂ (P-25) for MB photocatalytic degradation under visible light irradiation. Complete removal of aqueous MB was realized after visible light irradiation for 170 min with Bi₂FeVO₇ as the photocatalyst. The reduction of the total organic carbon (TOC) and the formation of inorganic products, SO ₄ ²⁻ and NO ₃ ⁻ revealed the continuous mineralization of aqueous MB during the photocatalytic course.     

Preparation of TiO<Subscript>2</Subscript> nanofibers immobilized on quartz substrate by electrospinning for photocatalytic degradation of ranitidine

The photocatalytic activity of TiO₂ nanofibers immobilized on quartz substrates was investigated by evaluating the decomposition of organic pollutants. TiO₂ nanofibers were synthesized by electrospinning the Ti-precursor/polymer mixture solution, followed by hot-pressing for enhancing the adhesion of TiO₂-nanofiber films to the substrates. TiO₂ started to crystalize in the anatase form at 500 °C and reached the optimal photocatalytic anatase/rutile phase ratio of 70:30 at a calcination temperature of 600 °C. The TiO₂-nanofiber film was demonstrated to be an efficient photocatalyst by ranitidine decomposition under UV illumination and was proven to have a comparable photocatalytic activity with the well-known Degussa P25 nanoparticulate photocatalyst and excellent recyclability during 10 cycles of photocatalytic operation, indicating no loss of TiO₂ nanofibers during photocatalytic operations.     

Photocatalytic reaction of arylamines/alcohols on TiO<Subscript>2</Subscript> nano-particles

In this article, the photocatalytic reaction of aniline and 4-amino N,N-dimethyl aniline with methanol, ethanol and isopropanol on anatase TiO₂ nano-particles under UV (365-nm wavelength) irradiation was examined. The concentration of unreacted arylamines and products was measured by gas chromatography picks integration, and then the products were identified by mass spectroscopy analysis. By making a comparison within the rates of photocatalysis of each arylamine in different alcohols under various irradiation times, it was revealed that, in all cases, the sequence of photocatalysis rate was methanol > ethanol > isopropanol. In reactions where the concentrations of arylamine were lower than 10 mmol/l, imines were the main products and the alkylation of amines was not observed. In the higher concentration of arylamines, oxidation and dimerization was occurred.     

TiO<Subscript>2</Subscript> photocatalytic oxidation: I. Photocatalysts for liquid-phase and gas-phase processes and the photocatalytic degradation of chemical warfare agent simulants in a liquid phase

The results of studies on the effect of the preparation procedure on the properties of TiO₂-based photocatalysts and the kinetics and mechanism of the photocatalytic oxidation of organic water pollutants are surveyed. The effects of calcination temperature, surface modification with platinum, and acid-base treatment of the surface of titanium dioxide on its activity in model gas-phase and liquid-phase reactions are considered. Optimal catalyst preparation conditions were found in order to achieve maximum activity, and conceivable reasons for the effects of the above factors on the activity were revealed. The intermediate products and mechanisms of the photocatalytic and dark reactions of solutes that simulated chemical warfare agents in water are considered. All of the test simulants can undergo complete oxidation to form inorganic products in an aqueous TiO₂ suspension under irradiation with UV light. It was found that, in addition to oxidation, the dark steps of hydrolysis also play an important role in the degradation of these substances. The low-frequency ultrasonic treatment (20 kHz) of a photocatalyst suspension in the course of the photocatalytic oxidation of dimethyl methylphosphonate can accelerate the reaction because of the facilitated transport of reactants to the surface of photocatalyst particles.__________Translated from Kinetika i Kataliz, Vol. 46, No. 2, 2005, pp. 203–218.Original Russian Text Copyright © 2005 by Vorontsov, Kozlov, Smirniotis, Parmon.     

Advanced Bi<Subscript>2</Subscript>O<Subscript>2.7</Subscript>/Bi<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> composite film with enhanced visible-light-driven activity for the degradation of organic dyes

Bi₂O_2.7/Bi₂Ti₂O₇ composite photocatalyst films are synthesized by sol–gel dip-coating. The ratio of adding Bi and Ti precursors can be controlled during the preparation process. The phase structure is confirmed by X-ray diffraction. The UV–visible diffuse reflectance spectrum shows that the composite catalysts present light absorption in the visible region. The obtained Bi₂O_2.7/Bi₂Ti₂O₇ composite films possess superior photocatalytic degradation of rhodamine B, owing to the visible light response of Bi₂O_2.7 and the separation of photogenerated electrons and holes between the two components. As a result, the Bi₂O_2.7/Bi₂Ti₂O₇ (Bi/Ti = 1:1) displays the highest photocatalytic activity under visible light or UV light irradiation for the degradation of different organic dyes, including methyl blue, methyl orange and acid orange 7.     

Solar light-driven photocatalytic production of hypochlorous acid over Pt/WO3 in seawater for marine antifouling

The hypochlorous acid (HCIO) was synthesized from seawater by the Pt/WO₃ photocatalyst under visible-light irradiation. The effect of WO₃ morphology and Pt loading on the performance of the composite photocatalyst for the production of HCIO has been studied in detail. The study found that among the series of materials, hollow WO₃ microspheres with a diameter of about 3 μm loaded with 1.0 wt% Pt have the best HCIO production performance. Over it, 14.52 μM of HClO (1.24 mg/L of free chlorine) was accumulated in 0.5 M NaCl solution after 2 h of visible-light photoirradiation. What is more, the concentration of HClO can reach 4.34 μM (0.354 mg/L free chlorine) in natural seawater for 1 h using this Pt/WO₃ photocatalyst. Under visible-light irradiation, the Pt/WO₃ photocatalyst has a good broad-spectrum antibacterial activity and the activity of inhibiting marine fouling algae. The Pt/WO₃ photocatalyst has high stability and reusability. All these characteristics are conducive to the application in the field of marine antifouling. Moreover, the photocatalytic reaction mechanism was evaluated by studying the photoelectrochemical properties of Pt/WO₃/FTO. This research provides a new strategy for replacing the traditional electrolytic marine antifouling system with the visible-light-catalyzed HClO production system.

     

Preparation of anatase phase titanium dioxide film by non-aqueous electrodeposition

The electrodeposition–annealing route to fabricating thin film of the promising photocatalyst material anatase-titanium dioxide (anatase-TiO₂) has been studied. The sample was deposited with a solution of N,N-dimethylformamide containing titanium compound by controlled-potential technique. SEM image showed the annealed sample at 600 °C for 1 h under air provided a continuous film with a thickness of ca. 350 nm. In this sample, X-ray photoelectron spectrum corresponding to the Ti 2p peak assigned to a chemical bond of TiO₂ and X-ray diffraction peaks assigned to the anatase phase were observed, respectively. Electrochemical oxidation in sodium sulfate solution on this annealed film was enhanced in the presence of UV light radiation. These results confirm the successful synthesis of photocatalytic anatase-TiO₂ film by the electrodeposition and annealing process.     

Photocatalytic reaction of aryl amines/alcohols on TiO<Subscript>2</Subscript> nanoparticles

In this article, the photocatalytic reaction of aniline and 4-amino N, N dimethyl aniline with methanol, ethanol and isopropanol on anatase TiO₂ nano-particles under UV (365 nm wavelength) irradiation was examined. The concentration of unreacted aryl amines and products was measured by gas chromatography picks integration, and then the products were identified by mass spectroscopy analysis. By making a comparison within the rates of photocatalysis of each aryl amine in different alcohols under various irradiation times, it was revealed that, in all cases, the sequence of photocatalysis rate was methanol > ethanol > isopropanol. In reactions where the concentrations of aryl amine were lower than 10 mmol/L, imines were the main products and alkylation of amines was not observed. In the higher concentration of aryl amines, oxidation and dimerization occurred.     

Enhancement of visible-light photocatalytic activity of Cu-doped TiO<Subscript>2</Subscript> nanoparticles

Bare TiO₂ and Cu-doped TiO₂ nanoparticles with different nominal doping amounts of Cu ranging from of 0.5 to 5.0 mol% were synthesized using the modified sol–gel method. The samples were physically characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer–Emmett–Teller-specific surface area, UV–Vis diffuse reflectance spectroscopy, zeta potential, X-ray photoelectron spectroscopy, inductively coupled plasma, and photoluminescence techniques. The Cu-doped TiO₂ exhibited good photocatalytic activity in mineralization of oxalic acid and formic acid under visible light irradiation. Photomineralization of oxalic and formic acids under visible light irradiation revealed greatly enhanced photoactivity exhibited by the 2.0 mol% Cu-doped TiO₂ photocatalyst compared to bare TiO₂ . The enhanced photocatalytic performance arises from copper ion doping in the TiO₂ structure, leading to an extended photoresponsive range, enhanced photogenerated charge separation, and transportation efficiency.