Simple fabrication and photocatalytic activity of S-doped TiO2 under low power LED visible light irradiation

A series of S-doped TiO₂ with visible-light photocatalytic activity were prepared by a simple hydrolysis method using titanium tetrachloride (TiCl₄) and sodium sulfate (Na₂SO₄) as precursors. The photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV–vis diffuse reflectance spectrophotometer (UV–Vis DRS), and X-ray photoelectron spectroscopy (XPS). With the doping of S, photocatalysts with small crystal size, high content of anatase phase were obtained. The result showed that S-doped TiO₂ demonstrate considerably high photoactivity under low power visible LED light irradiation, while undoped TiO₂ and the Degussa P25 have nearly no activity at all. The possible mechanism of S-doped for the visible-light activity was discussed.     

Construction of Z-scheme type CdS–Au–TiO2 hollow nanorod arrays with enhanced photocatalytic activity

The Z-scheme type CdS–Au–TiO₂ hollow nanorod arrays have been constructed on glass substrates by following these simple steps: firstly, highly ordered TiO₂ hollow nanorod arrays (THNAs) were synthesized by liquid phase deposition (LPD) using ZnO nanorod arrays as templates; then both Au core and CdS shell nanoparticles were achieved on the THNAs by in situ photodeposition. The prepared three-component films were characterized by field-emission scanning electron microscopy (FSEM), high-resolution transmission electron microscope (HRTEM), Raman scattering and ultraviolet–visible absorption spectrum. The results showed that Au–CdS core–shell nanoparticles were well dispersed on wall of anatase THNAs from top to bottom. The three-component nanojunction system was evaluated for their photocatalytic activity through the degradation of methylene blue (MB) in aqueous solution. It was found that the CdS–Au–TiO₂ three-component hollow nanorod arrays exhibited significantly enhanced photocatalytic activity compared with single (THNAs) and two components (Au-THNAs or CdS-THNAs) systems. Reasons for this enhanced photocatalytic activity were revealed by photoluminescence (PL) results of our samples.     

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.     

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 hollow TiO2@g-C3N4/Co3O4 core-shell microspheres for effective photooxidation degradation of tetracycline and MO

Traditional bulk photocatalysts often experience serious charge recombination and poor visible-light capturing, resulting in inefficient photocatalytic activity. However, proper nanostructure design usually helps to increase the activity of composite photocatalysts. Here, hollow TiO₂@g-C₃N₄/Co₃O₄ core-shell microspheres are first reported. The hollow structure of the heterostructured will directionally separate the photogenerated carriers, and the photogenerated holes transferred to the surface will be further captured by Co₃O₄ to achieve an exposed oxidized surface. The novel multi-stage hollow microspheres can simultaneously achieve effective transfer of photogenerated carriers and extended light absorption. Benefiting from these structural and compositional characteristics, the optimized TiO₂@g-C₃N₄/Co₃O₄ nanospheres have excellent photodegradation activity for tetracycline and MO. Under simulated sunlight, the degradation rates of TC (10 mg/L) and MO (25 mg/L) at 60 min are 91.6% and 97.8%, respectively. At the same time, high activity is maintained after multiple cycles of testing. Possible transfer paths for photogenerated carriers have also been proposed. This work will provide more inspiration for the design of multi-stage hollow photocatalytic systems.     

Hybrid photocatalysts for the degradation of trichloroethylene in air

Hybrid photocatalysts based on an adsorbent SiMgOx and a photocatalyst TiO₂ were developed in a plate shape. The ceramic surface was coated with TiO₂ by the slip-casting technique. The effect of the support in the photocatalytic degradation of trichloroethylene (TCE) was analyzed by modifying TiO₂ loading and the layer thickness. Photocatalysts were characterised by N₂ adsorption–desorption, mercury intrusion porosimetry, SEM, UV–vis spectroscopy and XRD. A direct relationship between the TiO₂ content and the photocatalytic activity was observed up to three layers of TiO₂ (0.66 wt.%). Our results indicate that intermediate species generated on the TiO₂ layer can migrate through relatively long distances to react with the OH⁻ surface groups of the support. By increasing the TiO₂ loading of the photocatalyst two effects were observed: trichloroethylene conversion is enhanced, while the efficiency of the oxidation process is decreased at expenses of increasing the selectivity to COCl₂ and dichloroacetylchloride (DCAC). The results are discussed in terms of the layer thickness, TiO₂ amount, TCE conversion and CO₂, and COCl₂ selectivity.     

Structure and photocatalytic performance of magnetically separable titania photocatalysts for the degradation of propachlor

A magnetic photocatalyst was prepared by modification of TiO₂ nanoparticles (Degussa P25) with nanocrystalline γ-Fe₂O₃ nanoparticles through a protective lining made up of two oppositely charged polyelectrolytes. As-prepared magnetically separable photocatalysts differing in γ-Fe₂O₃ loading (3, 8, 13, 20 and 30 wt.%) were characterized by XRD, TEM, thermal analysis, Mössbauer and magnetic measurements. The photocatalytic efficiency of the nanocomposite catalysts was evaluated using a chloroacetanilide herbicide (propachlor) in water as model compound. The primary degradation of propachlor followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. Generally, all magnetic photocatalysts exhibit good catalytic activity towards organic pollutants, do not suffer from photodissolution and can be reused several times without any decrease in their photocatalytic activity.     

Highly active TiO2−x−yNxFy visible photocatalyst prepared under supercritical conditions in NH4F/EtOH fluid

A novel N and F co-doped TiO₂ (TiO_2−x−yN_xF_y) photocatalyst is prepared by treating the TiO₂ precursor in NH₄F/ethanol fluid under supercritical conditions. During photocatalytic degradation of methylene blue under visible light irradiation, the as-prepared TiO_2−x−yN_xF_y exhibits higher activity than the undoped TiO₂, N-doped TiO₂ (TiO_2−xN_x), and F-doped TiO₂ (TiO_2−yF_y). Based on the characterizations including XRD, Raman, FTIR, TEM, PLS, UV–vis DRS, N₂ adsorption–desorption isotherms, XPS and NH₃-TPD, the synergetic promotions of N- and F-dopants incorporated into the TiO₂ lattice are discussed based on the enhanced spectral response in visible region, oxygen vacancies, and surface acidic sites. Meanwhile, the supercritical treatment also promotes the activity owing to the increase in both the surface area and the crystallization degree of anatase, and the enhanced incorporation of N- and F-dopants into the TiO₂ lattice.     

Photo-catalytic degradation of Rhodamine B on C-, S-, N-, and Fe-doped TiO2 under visible-light irradiation

C-, S-, N-, and Fe-doped TiO₂ photocatalysts were synthesized by a facile sol–gel method. The structure and properties of catalysts were characterized by N₂ desorption–adsorption, X-ray diffraction (XRD), UV–vis spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results revealed that the surface area of the multi-doped TiO₂ was significantly increased and the crystallite size was smaller than the pure TiO₂ obtained by a similar route. Compared with TiO₂, the peak position in doped-TiO₂ XRD patterns was slightly shifted, which could be attributed to the distortion by the substitution of carbon, nitrogen, and sulfur dopants for some oxygen atoms and Fe³⁺ for Ti⁴⁺ in the lattice of TiO₂. These substitutions were confirmed by XPS. In addition, these dopants were responsible for narrowing the band gap of TiO₂ and shifting its optical response from ultraviolet (UV) to the visible-light region. The photocatalytic reactivities of these multi-doped TiO₂ catalysts were investigated by degrading Rhodamine B (RB) in aqueous solution under visible-light irradiation (λ > 420 nm). It was found out that the reactivity was significantly enhanced and the catalyst doped with nitrogen, carbon, sulfur, and 0.3 wt% iron had the highest photocatalytic activity.     

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.     

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

A simple and straightforward approach to prepare TiO₂-coated carbon nanotubes (CNTs) is presented. Anatase TiO₂ nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO₂ molar ratio on the adsorption capability and photocatalytic efficiency under UV–visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO₂ NPs-coated CNTs photocatalysts. The TiO₂ NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO₂.     

Prevention of photocatalytic deterioration of resins using TiO2 pillared fluoromica

The TiO₂ pillared fluoromica powder was kneaded with polylactic acid resin. The composite showed high photocatalytic activity for degradation of acetaldehyde and toluene gas, especially at the range of 1–3 wt.% pillared mica powder, and this photocatalytic activity was higher than that of resins containing even higher amounts of commercial TiO₂ (P-25, Degussa). The composite test pieces of pillared mica showed smaller photocatalytic deterioration than the samples with P-25 powder in out-door weathering tests. Thus, the TiO₂ pillared clay resin composite shows excellent prevention of photocatalytic deterioration and high photocatalytic activity in comparison with P-25.     

Photocatalytic oxidation of toluene to benzaldehyde over anatase TiO2 hollow spheres with exposed {001} facets

A new series of anatase TiO₂ hollow structures were prepared by a facile hydrothermal process. When the hydrothermal time was increased from 20 min to 72 h, the resulting TiO₂ solid spheres gradually transformed into TiO₂ hollow spheres with higher surface crystallinity and exposed {001} facets. The as-prepared TiO₂-72 h sample exhibited the highest activity comparing to other TiO₂-based samples and commercial product Degussa P-25 towards the selective photocatalytic oxidation of toluene to benzaldehyde. Such great photocatalytic performance was mainly attributed to enhanced UV-adsorption and better charge separation efficiency due to higher surface crystallinity of TiO₂-72 h.     

Photocatalytic degradation of toluene over doped and coupled (Ti,M)O2 (M = Sn or Zr) nanocrystalline oxides: Influence of the heteroatom distribution on deactivation

In this work, we have studied the photocatalytic oxidation (PCO) of toluene over Sn- and Zr-doped TiO₂, and coupled TiO₂/SnO₂ and TiO₂/ZrO₂ catalysts. The TiO₂ sample doped with Sn (8% of metal ions) is composed by the anatase and rutile phases of TiO₂, while the Zr-doped sample (same dopant content) contains only the anatase phase. The coupled photocatalysts are formed, in addition to the phases present in their doped counterparts, by a segregated MO₂ phase (M: Sn or Zr). For the photocatalytic degradation of toluene, higher rates in the stationary state are obtained with the coupled catalysts with respect to the doped ones and the TiO₂ references (both synthetic and Degussa P25). In the case of the coupled photocatalysts, these higher rates are due to the absence of the deactivation that does occur for the rest of samples. Fresh and used photocatalysts have been studied by FTIR and EPR spectroscopies and by solid/liquid extraction in methanol, followed by GC/MS analysis. The obtained results lead us to conclude that, while structural and electronic modifications, due to the guest cations, are responsible for the high activity of doped samples observed in previous studies for a reaction not causing catalyst deactivation (methylcyclohexane PCO), other factors are crucial for the PCO of toluene. For this reaction, there is a relationship between surface water, adsorbed intermediates and resistance to deactivation, and thus the modifications in the amount and arrangement of surface water molecules caused by the second oxide may be the cause of the high degradation rate obtained with the coupled TiO₂/SnO₂ and TiO₂/ZrO₂ photocatalysts.     

A novel deposition precipitation method for preparation of Ag-loaded titanium dioxide

Ag/TiO₂ photocatalysts were prepared by a novel deposition precipitation method. Formation of Ag nanoparticles on the surface of TiO₂ was confirmed by XRD, HRTEM and XPS. The photocatalytic activity of Ag/TiO₂ was tested with the photocatalytic degradation of methyl orange and found effectively enhanced. The optimum content of Ag for photocatalytic activity is about 2.0 wt%.     

Preparation of cobalt coated TiO2 and WO3–TiO2 nanotube films via photo-assisted deposition with enhanced photocatalytic activity under visible light illumination

Highly ordered TiO₂ and WO₃–TiO₂ nanotubes were prepared by one-step electrochemical anodizing method and cobalt has been successfully deposited on these nanotubes by photo-assisted deposition process. The morphology, crystal structure, elemental composition and light absorption capability of samples were characterized by field emission scanning electron microscope, X-ray diffraction, energy dispersive X-ray spectrometer and ultraviolet–visible spectroscopy methods. All cobalt loaded samples show an appearance of red shift relative to the unloaded samples. The degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of these novel visible-light-responsive photocatalysts. Results showed that the photocatalytic activity of bare WO₃–TiO₂ samples is higher than that with undoped TiO₂ sample. Compared with unmodified TiO₂ and WO₃–TiO₂, the Co/TiO₂ and Co/WO₃–TiO₂ samples exhibited enhanced photocatalytic activity in the degradation of methylene blue. Kinetic research showed that the reaction rate constant of Co/WO₃–TiO₂ is approximately 2.26 times higher than the apparent reaction rate constant of bare WO₃–TiO₂. This work provides an insight into designing and synthesizing new TiO₂–WO₃ nanotubes-based hybrid materials for effective visible light-activated photocatalysis. The catalysts prepared in this study exhibit industrially relevant interests due to the low cost and high photocatalytic activity.     

First-principles study on transition metal-doped anatase TiO2

The electronic structures, formation energies, and band edge positions of anatase TiO₂ doped with transition metals have been analyzed by ab initio band calculations based on the density functional theory with the planewave ultrasoft pseudopotential method. The model structures of transition metal-doped TiO₂ were constructed by using the 24-atom 2 × 1 × 1 supercell of anatase TiO₂ with one Ti atom replaced by a transition metal atom. The results indicate that most transition metal doping can narrow the band gap of TiO₂, lead to the improvement in the photoreactivity of TiO₂, and simultaneously maintain strong redox potential. Under O-rich growth condition, the preparation of Co-, Cr-, and Ni-doped TiO₂ becomes relatively easy in the experiment due to their negative impurity formation energies, which suggests that these doping systems are easy to obtain and with good stability. The theoretical calculations could provide meaningful guides to develop more active photocatalysts with visible light response.     

Self-organized vanadium and nitrogen co-doped titania nanotube arrays with enhanced photocatalytic reduction of CO2 into CH4

Self-organized V-N co-doped TiO₂ nanotube arrays (TNAs) with various doping amount were synthesized by anodizing in association with hydrothermal treatment. Impacts of V-N co-doping on the morphologies, phase structures, and photoelectrochemical properties of the TNAs films were thoroughly investigated. The co-doped TiO₂ photocatalysts show remarkably enhanced photocatalytic activity for the CO₂ photoreduction to methane under ultraviolet illumination. The mechanism of the enhanced photocatalytic activity is discussed in detail.     

Photocatalytic Degradation of Organic Pollutants Under Visible Light Irradiation

Several TiO₂-based photocatalytic systems that have considerable visible light response have been developed, such as the photodegradation of organic pollutants on sensitized TiO₂ by visible light, construction of visible-light-active novel TiO₂ photocatalysts by matrix or surface modification. In this paper, we review briefly our recent progress in the TiO₂ photocatalytic degradation of organic pollutants by visible light, some related work by other groups is also involved.     

Synthesis and characterization of mesoporous Ta2O5–TiO2 photocatalysts for water splitting

Two series of Ta₂O₅–TiO₂ photocatalysts (Ta:Ti = 4:1, 1:1 and 1:4) were prepared by sol–gel technique applying triblock copolymer of Pluronic P123 and were tested in platinized form (0.3 wt.%) in photodecomposition of water under ultraviolet and visible light (λ > 300 nm). It was found the mesoporous character of tantalum containing catalysts with relatively high surface area (100–130 m² g⁻¹) of these samples. However, higher concentration of TiO₂ in mixed oxides leads to the destruction of mesoporous character of synthesized photocatalysts. All samples were characterized with thermogravimetry, XRD, N₂ physisorption, DR-UV–vis and FTIR spectroscopy. The mixed oxides of Ta₂O₅–TiO₂ system showed much lower band-gap than pure Ta₂O₅ and relatively high activity in platinized state in photocatalytic hydrogen generation under visible. Doping of pure oxides and mixed systems with sulfur resulted in lowering of the band-gap values below 3 eV and much better activity in H₂ evolution reaction. Non-platinized photocatalysts showed activity in liquid phase cyclohexene photooxidation at 305 K.