Synthesis and characterisation of Gd-doped mesoporous TiO2 materials

Using multi-walled carbon nano-tubes (MWNTs) as the template, Gd³⁺-doped mesoporous TiO₂ (M-TiO₂) material was prepared by the homogeneous precipitation-assisted template method. The as-prepared photo-catalysts were characterised using X-ray diffraction, scanning electron microscopy, nitrogen adsorption/desorption and ultraviolet-visible (UV-vis) diffuse-reflection spectroscopy analyses. The photo-catalytic properties of Gd³⁺-doped M-TiO₂ were primarily investigated by the photo-degradation of methyl orange under Xe-lamp irradiation and compared with those of pure M-TiO₂ and the commercial photo-catalyst Degussa P25. The results showed that the as-synthesised samples were of anatase crystalline phase and had red shifts in their UV-vis patterns with different Gd³⁺-doping concentrations. Gd³⁺-adding at 0.12 mol% could significantly enhance the photo-catalytic properties of the M-TiO₂ material and the rate of photo-degradation of methyl orange reached 97.3% under Xe-lamp irradiation for 150 min.     

Understanding the solar photo-catalytic activity of TiO2-ITO nanocomposite deposited on low cost substrates

In this work, we report on the photo-catalytic properties of TiO₂-ITO nanocomposite deposited on low cost conventional clay ceramic substrates. The nanocomposite was formed by spraying a solution prepared from the P25 TiO₂ powder (Degussa) mixed with an organometallic paste of a dissolved combination of indium and tin. A TiO₂-ITO powder-like nanocomposite was prepared for X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterization. The mean particle size of the TiO₂-ITO nanocomposite was found to be larger than that of pure TiO₂. The optical features of TiO₂-ITO-based layers (deposited on glass substrates) were investigated using UV-vis spectroscopy. The TiO₂-ITO nanocomposite deposited layers were found to have higher light absorption than the P25 TiO₂ powder. The photo-catalytic properties of the TiO₂-ITO nanocomposite (deposited on low cost clay ceramic substrates) were tested under solar irradiation using a well-known polluting dye. It was shown that the TiO₂-ITO nanocomposite exhibits higher degradation rates towards the pollutant dye than the P25 TiO₂ powder. The optical band gap of the TiO₂-ITO nanocomposite (2.79 eV) was found to be lower than that of pure TiO₂ (3.1 eV), while ITO (indium tin oxide) has a band gap of about 4.2 eV. ITO was found to be entirely transparent to sun light, while it exhibits a slight photo-catalytic activity, signifying the possible existence of an indirect photo-catalysis phenomenon (sensitized semiconductor photocalysis) and potential degradation (oxidation) of the pollutant through electron transfer from the dye to conduction band of the semiconductor. All photo-catalytic activity results were discussed in light of the optical band gap of the various compounds.     

Sonodegradation and photodegradation of methyl orange by InVO4/TiO2 nanojunction composites under ultrasonic and visible light irradiation

The InVO₄/TiO₂ nanojunction composites with different weight ratio of 1:10, 1:25, 1:50 and 1:100 were successfully constructed using an ion impregnate method, followed by calcining temperature 400 °C for 2 h in Ar. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were evaluated through the degradation of methyl orange (MO) in aqueous solution under ultrasonic and visible light irradiation, respectively. The experimental results determined that the (1:50) InVO₄/TiO₂ nanojunction composite has exhibited the highest sonocatalytic activity. It can be ascribed to vectorial charge transfer at the co-excited InVO₄/TiO₂ interface under ultrasonic irradiation, results in the complete separation of electrons and holes. Interestingly, the (1:25) InVO₄/TiO₂ nanojunction composite displayed superior photocatalytic activity for MO degradation under visible light, indicating that InVO₄ as a narrow band gap sensitizer can expand photocatalytic activity of TiO₂ to visible region, and the charge transfer can be formed from high energy level of InVO₄ conduction band to the low energy level of TiO₂ conduction band in a present of excited InVO₄ alone under visible light irradiation. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were found to be dependent significantly on different InVO₄ contents, which can be explained by the influence of charge transfer on the basis of the work functions of different catalysis mechanism.     

Gallium- and iodine-co-doped titanium dioxide for photocatalytic degradation of 2-chlorophenol in aqueous solution: Role of gallium

Visible-light-driven TiO₂-based catalysts for the degradation of pollutants have become the focus of attention. In the present work, iodine-doped titania photocatalysts (I-TiO₂) were improved by doping with gallium (Ga,I-TiO₂) and the resulting physicochemical properties and photocatalytic activity were investigated. The structural properties of the catalysts were determined by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and transmission electron microscopy. We found that Ga probably enters the TiO₂ framework for doping levels <0.5 mol%. A further increase in Ga content probably leads to dispersal of excess Ga on the TiO₂ surface. The photocatalytic activity of Ga,I-TiO₂ catalysts was evaluated using 2-chlorophenol (2-CP) as a model compound under visible and UV-vis light irradiation. The results indicate that 0.5 mol% Ga loading and calcination at 400 °C represent optimal conditions in the calcining temperature range 400-600 °C and with doping levels from 0.1% to 1 mol%. The effective enhancement of 2-CP degradation might be attributed to the formation of oxygen vacancies by Ga doping, which could decrease the recombination of electron-hole pairs.     

Efficient visible-light-induced photocatalytic degradation of MO on the Cr-nanocrystalline titania-S

In order to improve visible light photocatalytic activities of the nanometer TiO₂, a novel and efficient Cr,S-codoped TiO₂ (Cr-TiO₂-S) photocatalyst was prepared by precipitation-doping method. The crystalline structure, morphology, particle size, and chemical structure of Cr-TiO₂-S were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) techniques, respectively. Results indicate that the doping of Cr and S, cause absorption edge shifts to the visible light region (λ > 420 nm) compare to the pure TiO₂, reduces average size of the TiO₂ crystallites, enhances desired lattice distortion of Ti, promotes separation of photo-induced electron and hole pair, and thus improves pollutant decomposition under visible light irradiation. The photocatalytic activities of Cr-TiO₂-S nanoparticles were evaluated using the photodegradation of methyl orange (MO) as probe reaction under the irradiation of UV and visible light and it was observed that the Cr-TiO₂-S photocatalyst shows higher visible photocatalytic activity than the pure TiO₂. The optimal Cr-TiO₂-S concentration to obtain the highest photocatalytic activity was 5 mol% for both of Cr and S.     

Aerosol-assisted flow synthesis of WxTi1−xO2 solid solution spheres with enhanced photocatalytic activity

In this paper, W_xTi_1−xO₂ solid solutions (x = 0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO₂ and the W_0.015Ti_0.985O₂ solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W_0.015Ti_0.985O₂ solid solution catalyst was about 15 times of that of the pure TiO₂ and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.     

Preparation, characterization and visible-light photocatalytic activity of AgI/AgCl/TiO2

In this paper, a novel composite photocatalyst AgI/AgCl/TiO₂ was prepared by ion exchange method and characterized by XRD, SEM and UV-Vis spectrometry. The as-prepared AgI/AgCl/TiO₂ composites show much higher photocatalytic activity than AgCl/TiO₂ and AgI/TiO₂ under visible-light irradiation (λ > 400 nm) in the process of methyl orange (MO) degradation. When the molar percentage of AgI to initial AgCl is 20% (sample SE-20%), the maximal degradation efficiency of MO has reached 85.8% after irradiation for 120 min. The enhancement of photocatalytic activity of the composite photocatalyst AgI/AgCl/TiO₂ will be attributed to its good absorption in the visible-light region, especially low recombination rate of the electron-hole pairs based on the photoluminescence (PL) spectra investigation of AgI/AgCl/TiO₂ and the matching band structures of AgI, AgCl and TiO₂. The detection of reactive species by radical scavengers displays that O₂⁻ and H₂O₂ are the main reactive species for the degradation of MO under visible-light irradiation. Moreover, PL analysis by using terephthalic acid (TA) as a probe molecule further reveals that OH can be negligible for the degradation of MO.     

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.     

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.     

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 TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ 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 Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ 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.     

The effect of surface modification by nitrogen plasma on photocatalytic degradation of polyvinyl chloride films

The solid-phase photocatalytic degradation of poly(vinyl chloride) (PVC) films was investigated under the ambient air in order to assess the feasibility of developing photodegradable polymers. Nitrogen plasma was used to modify PVC films to enhance the photocatalytic degradation of PVC with nano-sized anatase TiO₂. The plasma parameter varied in this study is discharge power from 30 to 120 W for a constant treatment time of 60 s and a constant gas pressure of 10 Pa. The photodegradation of the plasma-treated PVC-TiO₂ films was compared with that of pure PVC films and PVC-TiO₂ films performing weight loss monitoring, scanning electron microscopy (SEM) analysis, contact angle measurements, electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The wettability of the plasma-treated PVC is improved significantly. ESR revealed that the signal of radicals on the surface of the plasma-treated PVC film was enhanced after the treatment. Furthermore, the weight loss indicated that TiO₂ speeds up the photocatalytic degradation of PVC chains. The SEM image of the plasma-treated PVC-TiO₂ film showed a lot of crack on the film surface after irradiation. XPS indicated that the C and Cl atomic concentration reached minimum values on the surface of plasma-treated PVC-TiO₂ under identical photocatalytic condition. The experimental results reveal that plasma treatment can obviously enhance the photocatalytic degradation of PVC.     

Preparation and characterization of iodine-doped mesoporous TiO2 by hydrothermal method

Iodine-doped mesoporous TiO₂ (I/TiO₂) was prepared by hydrothermal method, using tetrabutyl titanate as precursor, potassium iodate as iodine sources. The as-prepared I/TiO₂ catalysts were characterized by UV-vis, XRD, TEM, BET, TG/DTA, XPS and photoluminescence (PL) spectroscopy. Production of OH radicals on the I/TiO₂ surface was detected by the PL technique using terephthalic acid as a probe molecule. The effects of hydrothermal reaction temperature, calcination temperature and iodine doping content on the structure and properties of the catalysts were investigated. The results showed that iodine-doped TiO₂ calcinated at 300 °C have good anatase crystal. The optimal hydrothermal conditions have been determined to be that reaction temperature 120 °C, calcinated temperature 300 °C and added 1.16 mmol iodine dopants. The average particle size of I/TiO₂ synthesized under optimal condition (I-3 sample) is about 3.9 nm. The I-3 photocatalyst contains 100% anatase crystalline phase of TiO₂. BET specific surface area of I-3 sample is184.8 m² g⁻¹ and is 3.67 times that of pure TiO₂ (50.37 m² g⁻¹). Iodine in I/TiO₂ catalyst mainly exists in the form of I₂, and photoactivity of I/TiO₂ catalyst in visible light comes from photosensitize of I₂. I/TiO₂ catalysis shows very high efficiency for the degradation of phenol under visible light.     

Enhanced cyclability of CdS/TiO2 photocatalyst by stable interface structure

CdS nanoparticles were in situ deposited on TiO₂ nanosheets and nanorods under hydrothermal conditions, respectively. The effect of CdS–TiO₂ interface structure on hydrogen production activity was mainly investigated under visible light irradiation. The results showed that the TiO₂ nanosheet-based CdS/TiO₂ showed a higher activity and a higher cyclability than the nanorod-based sample due to the stronger interaction of CdS with the (0 0 1) facets of TiO₂ than with the (1 0 1) facets. It was proposed that the strong interaction between CdS nanoparticles and TiO₂ nanosheets effectively refrains the recombination of electrons and holes.     

Synthesis and photocatalytic properties of porous TiO2 films prepared by ODA/sol-gel method

Porous TiO₂ films were deposited on SiO₂ pre-coated glass-slides by sol-gel method using octadecylamine (ODA) as template. The amount of ODA in the sol played an important role on the physicochemical properties and photocatalytic performance of the TiO₂ films. The films prepared at different conditions were all composed of anatase titanium dioxide crystals, and TiO₂ crystalline size got larger with increasing ODA amount. The maximum specific surface area of 41.5 m²/g was obtained for TiO₂ powders prepared from titanium sol containing 2.0 g ODA. Methyl orange degradation rate was enhanced along with increasing ODA amount and reached the maximal value at 2.0 g addition of ODA. After 40 min of UV-light irradiation, methyl orange degradation rate reached 30.5% on the porous film, which was about 10% higher than that on the smooth film. Porous TiO₂ film showed almost constant activity with slight decrease from 30.5% to 28.5% after 4 times of recycles.     

Preparation, structure and photo-catalytic performances of hybrid Bi2SiO5 modified Si nanowire arrays

Bi₂SiO₅ modified Si nanowire array films were fabricated as photo-catalysts via dip-coating Bi(NO₃)₃ on silver-assisted electroless wet chemical etching Si nanowires and subsequently annealing. The structures and morphologies of as-prepared samples are characterized by X-ray diffraction, Fourier transform infrared spectrum, scanning electron microscopy and transmission electron microscopy. The results of photocatalytic experiments indicated that the Bi₂SiO₅ modified Si nanowire arrays benefit the improvement for efficient electron-hole separation and photo-catalytic stability, thereby possessing superior photo-degradation performance. These hybrid nanowire arrays will be promising materials for photo-catalysts and degradation agents.     

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.     

Characteristics and heterostructure of metal-doped TiO2/ZnO nanocatalysts

In this study, Ag or Al-doped TiO₂/ZnO heterostructure nanocatalysts were prepared using a sol-gel method for photocatalysis to evaluate the degradability. The photocatalytic behavior was evaluated by the degradation of methylene blue (MB) under ultraviolet (UV) light irradiation. Photocatalytic studies suggested that 1 mol% Ag-doped TiO₂/ZnO (TiO₂/ZnO = 0.75/0.25) heterostructure nanocatalysts showed higher photocatalytic activity, and that the degradation efficiency can reach 83% in 4 h, 14% higher than that for pure TiO₂. Finally, the photocatalysis mechanism for the Ag-doped TiO₂/ZnO heterostructure nanocatalysts is discussed.     

Design and fabrication of a TiO2/nano-silicon composite visible light photocatalyst

Nano-silicon (nc-Si) was utilized as the charges generator to promote the photocatalytic and super-hydrophilic reactivity of TiO₂ film under visible light irradiation. The photocatalytic ability of TiO₂/nc-Si composite photocatalyst was evaluated by a set of experiments to photodecompose 100 ppm methylene blue (MB) in aqueous solution. And the super-hydrophilic property was characterized by measuring the water droplet contacts angle, under visible light irradiation in atmospheric air and at room temperature. Under 100 mW/cm² visible light irradiation, the droplet contact angles were reduced to 0° within 4 h with nc-Si charge generator. Additionally, the rate constant of MB photo-degradation was promoted 6.6 times.     

Photocatalytic activity enhancement of Dy-doped TiO2 nanoparticles hybrid with TiO2 (B) nanobelts under UV and fluorescence irradiation

The main drawbacks of anatase titanium dioxide (TiO₂) nanoparticles for being used as a photocatalyst are due to the rapid charge recombination of the electron-hole pairs and the wide band gap energy, limiting its photocatalysis application. To enhance photocatalytic activity, structure modification was performed here. Heterogeneous nanostructure of Dy-doped TiO₂ nanoparticles hybrid with Monoclinic TiO₂ nanobelts (Dy/TNBs) was fabricated via hydrothermal method. Annealing temperature was varied to investigate its effect on phase composition and morphology of the as-prepared TiO₂ catalyst. Phase composition and morphology were studied by XRD and SEM, respectively. The effect of amount of catalyst loaded on the degradation efficiency of methylene blue (MB) dye in aqueous solution under UV and fluorescence illumination was investigated. The results showed that pure monoclinic TiO₂ nanobelts (TNBs) was achieved at 450 °C. Enhanced photocatalytic activity under both UV and fluorescence irradiation was found on Dy/TNB samples. The optimum Dy dosage providing the highest MB degradation rates under both irradiation sources was 0.1 mol%.     

TiO2 activation using acid-treated vermiculite as a support: Characteristics and photoreactivity

Vermiculite was treated by sulfuric or nitric acid aqueous solutions with different concentration. These modified materials as the promising supports, were used to immobilize TiO₂. TiO₂ was prepared by the precursor, which was obtained by substituting partly isopropyl alcohol with Cl⁻ in titanium chloride {[Ti(IV)(OR)_nCl_m] (n = 2-3, m = 4 − n)}. The TiO₂/vermiculite composites were characterized by X-ray diffraction, scanning electron microscopy, and the nitrogen absorption. Their photocatalytic activity was evaluated by removal of methylene blue (MB). The pure anatase type crystalline phase was well deposited on the supports. The concentrations of acid for treatment had a significant influence on pore sizes and surface area of vermiculite. The treatment process changed microstructure of vermiculite, modified its characteristics, and farther improved the catalytic activity and absorption capacity of TiO₂/vermiculite composites. The treatment effect of nitric acid was superior to that of sulfuric acid.