等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

A new coral structure TiO2/Ti film electrode applied to photoelectrocatalytic degradation of Reactive Brilliant Red

A novel structure TiO₂/Ti film was prepared on a titanium matrix using anodic oxidation technique and applied to degrade Reactive Brilliant Red (RBR) dye in simulative textile effluents. The film was characterized by Field-Emission Scanning Electron Microscope (FE-SEM), Laser Micro-Raman Spectrometer (LMRS), UV–vis spectrophotometer (UVS) and Photoelectrocatalytic (PEC) experiment. The results show that the surface morphology of the film is coral structure, and the crystal structure of the film is anatase. The absorbency of the coral structure TiO₂/Ti film is 87–93% in the UV light region, and 77–87% in the visible light region. PEC experiment indicates that the photocurrent density of the coral structure TiO₂/Ti film electrode achieves 160 μA/cm². The color and Chemical Oxygen Demand (COD) removal efficiencies of RBR achieve 73% and 60% in 1 h, respectively. These are 16% and 58% higher than those of nanotube TiO₂/Ti film electrode. These were attributed to that these electrodes with different surface morphologies exhibit distinct surface areas and light absorption rate.     

Influence of annealing on the structure and stoichiometry of europium-doped titanium dioxide thin films

This work presents the influence of annealing on the structure and stoichiometry of europium (Eu)-doped titanium dioxide (TiO₂). Thin films were fabricated by magnetron sputtering from a metallic Ti-Eu target in oxygen atmosphere and deposited on silicon and SiO₂ substrates. After deposition the selected samples were additionally annealed in air up to 1070 K.Film properties were examined by means of X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) and the results were analyzed together with the undoped TiO₂ thin films prepared under similar technological conditions.XRD results showed that depending on the Eu content, as-deposited thin films consisted of the TiO₂-anatase or TiO₂-rutile.An additional annealing will result in the growth of anatase crystals up to 35 nm, but anatase to rutile phase transformation has not been recorded. AFM images display high quality and a dense nanocrystalline structure. From the XPS Ti2p spectra the 4+oxidation state of Ti was confirmed. The O1s XPS spectra displayed the presence of an O²⁻ photoelectron peak accompanied by an additional broader peak that originates from hydroxyl species chemisorbed at the sample surface. It has been found that Eu dopant increases the OH⁻ content on the surface of prepared TiO₂:Eu thin films. The calculated O/Ti ratio was in the range of 1.85-2.04 depending on the sample.     

Optical properties of TiO2 thin films after Ag ion implantation

Metal plasma ion implantation has being successfully developed for improving the electronic and optical properties of semiconductor materials. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. The TiO₂ thin film was optimized to obtain a high-purity crystalline anatase phase by calcinations at 550 °C. The TiO₂ coating was uniform without aggregation, which provided good photo conversion efficiency. Ag ion implantation into the as-calcined TiO₂ thin films was conducted with 1 × 10¹⁵ ~ 1 × 10¹⁶ ions/cm² at 40 keV. The peak position and intensity of the photoluminescence and UV-Vis absorption spectra are quite sensitive to Ag doping. The optical characterization showed a shift in optical absorption wavelength towards infrared ray side, which was correlated with the structure variation of the Ag⁺ implanted TiO₂. Due to the strong capability of forming compounds between the energetic silver ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

Influence of silver doping on the phase transformation and crystallite growth of electrospun TiO2 nanofibers

Ag doped TiO₂ nanofibers were fabricated by electrospinning technique using polyvinyl pyrrolidone (PVP) and titanium isopropoxide (TiP) as precursor. The effects of silver and calcination temperature on the preparation of electrospun TiO₂ nanofibers were investigated. The calcination temperature determines the TiO₂ phases as ether anatase or rutile. When the calcination temperature increased, crystallite size of TiO₂ nanofiber increased. The crystallite size of Ag doped TiO₂ nanofiber is smaller than that of the pure TiO₂ nanofiber because silver is retrained in this phase transformation. Silver controlled the phase transformation as well as had an inhibition effect on the growth of anatase crystallite.     

Fabrication of porous TiO2 film via hydrothermal method and its photocatalytic performances

Porous anatase (TiO₂) films were fabricated onto stainless steel substrates with Ti(OC₄H₉)₄ as a precursor via hydrothermal process. The crystallization and porous structure of TiO₂ film were dependent on the time and temperature of the hydrothermal reaction. A TiO₂ film with orderly porous structure and high crystallization was obtained upon treatment at 150 °C for 2 h. The grain size of TiO₂ is ca. 6 nm, and pore diameter is ca. 10 nm. Diffusion of Fe into the porous TiO₂ film occurred; Fe also diffused onto the surface of the film with the extension of hydrothermal reaction time or increase of the reaction temperature. The diffusion reaction has a large effect on the formation of porous TiO₂ film as well as its interface texture. However, it does not change the crystal phase of the TiO₂. The resultant TiO₂ film showed high photocatalytic activity towards degradation of gaseous formaldehyde.     

Hydrothermal growth of rutile TiO2 nanorod films on titanium substrates

Rutile TiO₂ nanorod films have been successfully prepared on titanium substrate via a hydrothermal method using Tetra-n-butyl titanate as Ti source in the presence of concentrated hydrochloric acid. The effect of Ti substrate annealing treatment and adding of additional alkali metal chlorides in hydrothermal solution on the growth of TiO₂ nanorod films has been studied using scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and water contact angle measurement. The growth mechanism of the TiO₂ nanorods on Ti substrate has also been discussed. It has shown that the initial rutile film transformed from anatase promotes the nucleation and epitaxial growth of rutile TiO₂ nanorods. The superior wettabilities of the TiO₂ nanorods resulted from treatments of vacuum and ultraviolet show great potential for applications in orthopaedic, dental implants, and possible photocatalysis.     

Preparation and photocatalytic activity of anatase TiO2 nanocrystallites with high thermal stability

Anatase TiO₂ nanocrystallites were prepared from TiCl₄ with addition of aqueous ammonia by changing Ti(OH)₄ hydrogel into its corresponding alcogel followed by supercritical drying in ethanol medium. The as-prepared TiO₂ was characterized by XRD, TG and BET. The results show that the prepared anatase TiO₂ has remarkable high thermal stability. The anatase structure of the prepared TiO₂ is maintained even after calcination up to temperatures as high as 800 °C. The photocatalytic activity of the prepared TiO₂ calcined at 800 °C in degradation of reactive brilliant red X-3B is comparable to commercially available nanosized P25 TiO₂.     

Influence of metal plasma ion implantation on photo-sensitivity of anatase TiO2 thin films

Nano-scale TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. The Ti(IV) butoxide-based TiO₂ thin films were optimized for transforming into the high-purity crystalline anatase phase when calcined at 500 °C. To further enhance the photo-catalysis sensitivity of TiO₂ thin films for use in visible light environments, a metal plasma ion implantation process was implemented to modify the band gap electron configuration of Ti. Various transition metal atoms such as Ni, Cu, V, and Fe were ionized and accelerated at 20 keV to impinge on the surface of TiO₂ substrates at a dosage of 5 × 10¹⁵ ions/cm². ESCA analysis confirmed the binding energy shift of Ti by 0.8-1.2 eV, which accounted for the increased effective positive charge of Ti, resulting in more effective electron trapping capability and, thus, the electron-hole pair separation. In addition, the absorption spectroscopy demonstrated that optical absorption in the visible light regime occurred in specimens implanted with transition metal ions, likely due to the formation of extra impurity energy levels within the original TiO₂ band gap energy structure. Among all tested implant materials, the band gap energy of TiO₂ was effectively reduced by Cu and Fe ion implantation by 0.9-1.0 eV, which was sufficient enough to excite valence electrons over the band gap in visible light environments. The feasibility of the metal-doped TiO₂ thin films for effective applications under visible light irradiation was further confirmed by using super-hydrophilicity contact-angle measurement.     

Preparation and photocatalytic activity of TiO2 powders from titanium citrate complex using two-step hydrothermal treatments

White, almost carbon-free TiO₂ powders were prepared from a titanium citrate complex ((NH₄)₄[Ti₂(C₆H₄O₇)₂(O₂)₂]·4H₂O) using a two-step hydrothermal treatment. The product yield, carbon contamination, and crystalline phase of TiO₂ depended on both the temperature and pH value for each treatment. Titanium was precipitated as a solid phase (H₂Ti₂O₅·H₂O) using the first hydrothermal treatment in the basic condition (pH = 12) at temperatures less than 150 °C. Then white rutile or anatase powder was crystallized using the second hydrothermal treatment at 200 °C. By changing the pH condition of the second hydrothermal treatment, rutile and anatase were synthesized selectively. The photocatalytic decomposition activity of obtained rutile powder for gaseous 2-propanol under visible light was increased by Cu-grafting.     

Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.     

Solar photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) using TiO2/SiO2 aerogel composite photocatalysts

Silica aerogels and TiO₂/silica aerogel composite photocatalysts were synthesized by sol–gel technique at ambient pressure using orthosilioate and tetra-n-butyl titanate as precursors, respectively. The prepared composite photocatalysts were characterized by XRD, TEM, BET surface area, FT-IR and UV–vis absorption spectra. The results showed that the TiO₂/silica aerogel composite photocatalysts possess high surface area. The addition of silica aerogels inhibited the grain growth and phase transformation of anatase to rutile during calcination. The TiO₂/silica aerogel composite sample calcined at 500 °C with an optimal silica aerogel content of 7 wt.% afforded the highest photocatalytic activity. The photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) was investigated by using this novel TiO₂/silica aerogel composite photocatalyst under solar light irradiation. The effects of irradiation time, pH, catalyst concentration, temperature and initial DNBP concentration were examined as operational parameters. The optimal operational parameters were found as follows: pH as solution pH 4.82, 8 g L⁻¹ catalyst concentration, 20 °C, and 240 min irradiation time. The kinetics of DNBP degradation by TiO₂/silica aerogel composite fit well a pseudo-first-order kinetic model. The repeatability of photocatalytic activity was also tested. This study showed the feasible and potential use of TiO₂/silica aerogel composite photocatalysts in degradation of toxic organic contaminants.     

Fabrication of light absorbing TiO2 μ-donuts

TiO₂ µ-donuts were fabricated on glass and silicon by sol-gel technique using a mask of PMMA nanopillars created by removing PS from a spin-coated composite polymer of PS and PMMA. X-ray diffraction confirmed the anatase TiO₂ phase. X-ray photoelectron spectra showed signals from Ti 2p_3/2 at 458.8 eV and O 1s at 530.4 eV confirming presence of TiO₂. The heights and diameters of the TiO₂ µ-donuts are ~ 353 nm and ~ 2.8 µm, respectively as revealed by atomic force microscopy. UV-vis absorption spectra of TiO₂ µ-donuts showed an unusual light absorption at ~ 524 nm making its potential use in solar-cell applications.     

Phase transformation in semi-transparent TiO2 films irradiated with CO2 laser

Anatase (TiO₂) thin films were obtained by immersion of glass plates into a titanium sol-gel precursor followed by calcination at 450 °C for 3 h. The Raman results for the CO₂ laser irradiated TiO₂ films show that laser radiation is able to promote favorable changes of anatase phase in anatase/rutile mixtures. Nevertheless, the transformation process level depends on laser characteristics and scan speed of the radiation treatment.     

The super-hydrophilicities of Bi–TiO2, V–TiO2, and Bi–V–TiO2 nano-sized particles and their benzene photodecompositions with H2O addition

This study focused on the super-hydrophilicities of metal-TiO₂ photocatalysts, including metals with three-oxidation and five-oxidation states, and their benzene photodecompositions with or without H₂O addition. The nanometer-sized metal-TiO₂s, including Bi³⁺, V⁵⁺, and Bi³⁺–V⁵⁺ ions, were prepared using a solvothermal method. The XRD result identified these to have pure anatase structures after solvothermal treatment at 200 °C for 10 h, without any treatment. The spherical particle sizes were distributed within the range of 10–50 nm after 500 °C calcinations, and the particle sizes decreased with an increase of the Bi component, while it increased with the V component compared with that of pure TiO₂. The XPS result showed that the peaks for O1s (Ti–O) shifted to the larger binding energy in Bi–TiO₂; on the other hand, it shifted to the smaller binding energy in V–TiO₂. In particular, the Ti–OH peak, which means to hydrophilicity, decreased with an increase of the Bi component; it increased, however, with the V component. The contact angle expressed about 3° on the Bi–TiO₂ nano-sized film (200-nm thickness) after irradiation for 2 h; otherwise, it approached 0° on the V–TiO₂ nano-sized film after 30 min. In particular, the decreased angle was continued under dark condition on the Bi–V–TiO₂ nano-sized film. The benzene photodecomposition in the batch system increased in the order of Bi (3.3)–V (6.7)–TiO₂ > V–TiO₂ > pure TiO₂ > Bi–TiO₂, and the maximum benzene conversion was 35% after 60 min. The conversion remarkably increased, however, in almost all catalysts with H₂O addition during the benzene photo-decomposed reaction, and in particular, the conversion reached up to 80% after 180 min in Bi–V–TiO₂. In the continuous system for Bi–V–TiO₂ with H₂O addition, the photodecomposition rate of 50% was maintained for 168 h, without catalytic deactivation. After photoreaction, there were minimal deposited cokes in the photocatalyst in both reaction conditions, with and without H₂O addition. The deposited amounts were smaller, however, in the reaction with H₂O addition. This result is a proof that photocatalytic deactivation can be retarded by an H₂O supplement during VOC decomposition.     

Field emission from the structure of well-aligned TiO2/Ti nanotube arrays

Well-aligned TiO₂/Ti nanotube arrays were synthesized by anodic oxidation of titanium foil in 0.5 wt.% HF in various anodization voltages. The images of filed emission scanning electron microscopy indicate that the nanotubes structure parameters, such as diameter, wall thickness and density, can be controlled by adjusting the anodization voltage. The peaks at 25.3° and 48.0° of X-ray diffraction pattern illuminate that the TiO₂ nanotube arrays annealed at 500 °C are mainly in anatase phase. The filed emission (FE) properties of the samples were investigated. A turn-on electric field 7.8 V/µm, a field enhancement factors approximately 870 and a highest FE current density 3.4 mA/cm² were obtained. The emission current (2.3 mA/cm² at 18.8 V/µm) was quite stable within 480 min. The results show that the FE properties of TiO₂/Ti have much relation to the structure parameters.     

Structure, conductivity, and optical absorption of Ag2−xO films

Evaporation of Ag in the presence of an electron cyclotron resonance (ECR) oxygen plasma was used to deposit Ag_2−xO films with a range of stoichiometries onto r-plane sapphire substrates. A quartz crystal oscillator (QCO) was used to accurately measure the silver and oxygen arrival rates and establish the O/Ag flux ratio needed to produce films with nominal Ag₂O stoichiometry. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis indicates that the Ag_2−xO films are not single phase but contain signatures of coexisting Ag₂O and AgO components. XRD shows that the lattice matching with the r-plane sapphire substrate causes the Ag₂O phase to grow with <002> heteroepitaxial crystallites coexisting with crystallites having <111> normal and random in-plane orientation. The AgO phase also forms with crystallites having <002> heteroepitaxy as well as crystallites with <111> normal and random in-plane orientation. The mixed phase Ag_2−xO films exhibit approximately 77% optical transmission over the visible range (500 nm to 700 nm) and have a single absorption edge near 3.3 eV. Four-point van der Pauw conductivity and Hall effect measurements indicate that the Ag_2−xO films are p-type with a conductivity on the order of 3 × 10^− 3 Ω^− 1 cm^− 1.