Effect of V doping concentration on the electronic structure,optical and photocatalytic properties of nano-sized V-doped anatase TiO2

V-doped TiO₂ with V/Ti ratio of 1–5% has been synthesized by hydrothermal method and then characterized by XRD, TEM, BET specific surface area, XPS and UV–vis. absorption spectra. The photocatalytic activity of the as-synthesized samples was investigated by the degradation of methylene blue in aqueous solution under visible light irradiation. Density functional theory (DFT) based calculations were performed to investigate the mechanism of band gap narrowing, the shift of light absorption edge, the location of V in the TiO₂ lattice and the variation in electronic and optical properties of TiO₂ with the increase of V doping concentration. Irrespective of the V doping concentration, TEM images indicate that all the doped samples were composed of equiaxed spherical anatase TiO₂ particles with good crystallinity and uniform particle size distribution. Both the experimental results from XPS survey and the theoretical calculation argue that the doped V replaces the lattice Ti and form substitutional impurity. The visible light absorption can be optimized by adjusting the V doping concentration. Among the doped samples with different V doping concentrations, the sample with V/Ti ratio of 2% depicts better visible light photocatalytic activity due to the enhanced visible light absorption and improved separation of electron–hole pairs.     

An efficient visible light photocatalyst prepared from TiO<Subscript>2</Subscript> and polyvinyl chloride

An efficient visible light photocatalyst has been prepared from TiO₂ nanoparticles and a partly conjugated polymer derived from polyvinyl chloride (PVC). It was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), UV–visible diffuse reflectance spectroscopy (UV–Vis DRS), Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The visible light photocatalytic activity of the as-prepared photocatalyst was evaluated by the photocatalytic degradation of Rhodamine B (RhB) under visible light irradiation. The XPS, FT-IR, and Raman spectra show that the partly conjugated polymer derived from PVC exists on the surface of the TiO₂ nanoparticles. The UV–Vis DRS, XRD, and TEM results reveal that the modification of the partly conjugated polymer can obviously improve the absorbance of the TiO₂ nanoparticles in the range of visible light and hardly affect their size and crystallinity. The visible light photocatalytic activity of the as-prepared TiO₂ nanocomposites is higher than that of commercial TiO₂ (Degussa P25) and comparable with those of visible light photocatalysts reported in the literature. Their visible light photocatalytic stability is also good. The reasons for their excellent visible light photocatalytic activity and the major factors affecting their photocatalytic activity are discussed.     

氮掺杂纳米TiO2粉体的制备研究

以锐钛矿相纳米TiO2粉体和盐酸胍的混合物为起始反应物，通过在不同温度条件下对反应物直接进行热处理制得了淡黄色的掺氮纳米TiO2粉体．采用XRD、BET、XPS、紫外-可见光漫反射对所制备的粉体进行了性能表征.XPS测试表明，掺氮粉体N1s的结合能峰位于396．9eV处，表明N原子以Ti-N键的形式存在于TiO2中，N原子进入了TiO2晶格，实现了掺杂．其中，在350℃、保温2．5h的条件下所制样品的掺氮量达到8．3％．XRD分析表明，实验制得的氮掺杂TiO2粉体在350、450、550、650℃热处理3h后仍为锐钛矿相；掺氮样品均具有好的紫外光吸收，且吸收边均红移至可见光区；350℃保温2．5h时具有最好的紫外-可见光响应，其吸收边红移至700nm左右．亚甲基蓝的可见光降解实验表明氮掺杂样品具有良好的可见光催化活性．     

Visible-light-active silver- , vanadium-codoped TiO<Subscript>2</Subscript> with improved photocatalytic activity

Optimized doped TiO₂ is necessary for efficient visible light harvesting and widening the applications spectrum of TiO₂-based materials. Titanium dioxide doped with silver and/or vanadium has been synthesized by one-pot hydrothermal method without post-calcination. Codoping induced visible light absorption while maintaining the photoactive anatase phase along with good crystallinity. Synthesized products are in nanometer range and possess high specific surface area. Having nearly spherical morphology, the particles are distributed and the particle size estimated from TEM observation is in accordance with the XRD results. Spectroscopic investigations reveal that the doped atoms successfully entered the TiO₂ lattice modifying the band structure. The narrowed band gap allows visible light photons for absorption, and the codoped samples displayed enhanced visible light absorption among the synthesized samples. Photodegradation performance evaluated under visible light irradiations showed that silver- , vanadium-codoped TiO₂ have the best visible light photocatalytic activity attributed to stable configuration, high visible light absorption, coupling between silver and vanadium and their optimal doping concentration.     

Optical and photocatalytic properties of the Fe-doped TiO2 nanoparticles loaded on the activated carbon

In this work, Fe-doped (1?wt%) TiO₂ loaded on the activated carbon nano-composite was prepared using a sol-gel method. A prepared nano-composite was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), BET surface area, Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL) spectroscopy and UV–Vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of the nano-composite was evaluated through degradation of synthetic textile wastewater, reactive red 198, under visible light irradiations. The XRD result indicated that the TiO₂ nano-composite contained only anatase phase. The surface area of the TiO₂ increased from 48?m²/g to 100?m²/g through the fabrication of the nano-composite. The FE-SEM results indicate that the TiO₂ particles with an average particle size of 35–70?nm can be deposited homogeneously on the activated carbon surface. DRS showed that the Fe doping in the TiO₂ -activated carbon nano-composite induced a significant red shift of the absorption edge and then the band gap energy decreased from 3.3 to 2.9?eV. Photocatalytic results indicated that the photocatalytic activity of the Fe doped TiO₂ increased under visible light irradiation in the presence of the activated carbon.     

Hydrothermal synthesis of hemisphere-like F-doped anatase TiO<Subscript>2</Subscript> with visible light photocatalytic activity

Hemisphere-like F-doped anatase TiO₂ has been synthesized by hydrothermal treatment of TiF₄ aqueous solution in the presence of starch at 130 °C for 10 h, and then calcined at 450 °C for 2.5 h in air. The as-synthesized product has been investigated by photocatalytic reaction test and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–Vis diffuse reflectance spectra (DRS). The results showed that fluorine was successfully doped into the TiO₂ hemispheres. The F-doped TiO₂ hemispheres showed high visible light activity in degradation of acid orange II, which could be attributed to the creation of oxygen vacancies and good crystallinity.     

Preparation and characterization of N–I co-doped nanocrystal anatase TiO2 with enhanced photocatalytic activity under visible-light irradiation

N–I co-doped TiO₂ nanoparticles were prepared by hydrolysis method, using ammonia and iodic acid as the doping sources and Ti(OBu)₄ as the titanium source. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and ultraviolet–visible diffuse reflection spectroscopy (UV–vis DRS). XRD spectra show that N–I–TiO₂ samples calcined at 673 K for 3 h are of anatase structure. XPS analysis of N–I–TiO₂samples indicates that some N atoms replace O atoms in TiO₂ lattice, and I exist in I⁷⁺, I⁻ and I⁵⁺ chemical states in the samples. UV–vis DRS results reveal that N–I–TiO₂ had significant optical absorption in the region of 400–600 nm. The photocatalytic activity of catalysts was evaluated by monitoring the photocatalytic degradation of methyl orange (MO). Compared with P25 and mono-doped TiO₂, N–I–TiO₂ powder shows higher photocatalytic activity under both visible-light (λ > 420 nm) and UV–vis light irradiation. Furthermore, N–I–TiO₂ also displays higher COD removal rate under UV–vis light irradiation.     

Preparation,characterization and photocatalytic activity of TiO2 codoped with yttrium and nitrogen

Nanocrystalline photocatalysts of TiO₂ codoped with yttrium and nitrogen were prepared by the sol–gel method and investigated by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), the Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), respectively. Slight red-shifts of the Raman peak at 144 cm^?1 were observed in the doped samples after the incorporation of Y³⁺ and N^3? into the lattice of TiO₂. The N doping caused the improvement of visible light absorption because of the formation of the N 2p states isolated above the valence band maximum of TiO₂. Whereas, the absorption property of the pure or N doped TiO₂ was depressed after the introduction of Y. The photocatalytic activities of the samples were evaluated by monitoring the degradation of methylene blue (MB) solution. The codoped sample with N and 0.05 at.% Y exhibited an enhanced photocatalytic efficiency. It is suggested that the charge trapping due to the Y doping and the visible light response due to the N doping are responsible for the enhanced photocatalytic performance in this sample. However, the photocatalytic activity of the codoped TiO₂ was suppressed step by step as the Y doping level increased, which could be attributed to the formation of photogenerated charge carriers recombination centers at the Y substituting sites.     

Visible light response and superior dispersed S-doped TiO2 nanoparticles synthesized via ionic liquid

Visible light response and superior dispersed S⁶⁺-doped TiO₂ nanoparticle catalysts (S-TiO₂) were prepared via ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate. The phenol was used for the evaluation of the S-TiO₂ photocatalytic activity. S-TiO₂ was characterized by XPS, UV–vis DRS, FE-SEM, TEM, XRD, TG/DSC, FTIR, and BET. The results showed that S-TiO₂ with appropriate S doping prepared via ionic liquid had smaller particle size, better dispersion, higher activity, and higher surface area (S_BET) than that prepared in water. Cationic S⁶⁺ incorporation into TiO₂ lattice substitutes for Ti⁴⁺ lattice site, generates Ti–O–S bonds in TiO₂, and leads to the formation of donor defect levels in band gap, so that the photocatalytic sensitization of TiO₂ has been extended to visible light region. The optimal content in S doping for the better photocatalytic performance can optimize electrical properties of the intrinsic n-type TiO₂ by adding the adequate amount of donor defect of S_Ti²⁺ for considering the lifetime of the photo-induced charge pairs.     

Phosphomolybdic acid-modified highly organized TiO2 nanotube arrays with rapid photochromic performance

TiO₂ nanotube arrays were prepared by means of an electrochemical anodization technique in an organic electrolyte solution doped with polyvinyl pyrrolidone (PVP) and were subsequently modified with phosphomolybdic acid (PMoA) to obtain PMoA/TiO₂ nanotube arrays. The microstructure and photochromic properties were investigated via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV–vis), and X-ray photoelectron spectroscopy (XPS). The results indicated that the Keggin structure of PMoA and the nanotube structure of TiO₂ were not destroyed, and there was a strong degree of interaction between PMoA and TiO₂ at the biphasic interface with lattice interlacing during the compositing process. The XPS results further indicated that there was a change in the chemical microenvironment during the formation process of the composite, and a new charge transfer bridge was formed through the Mo-O-Ti bond. Under visible light irradiation, the colorless PMoA/TiO₂ nanotube array quickly turned blue and exhibited a photochromic response together with reversible photochromism in the presence of H₂O₂. After visible light irradiation for 60 s, the appearance of Mo⁵⁺ species in the XPS spectra indicated a photoreduction process in accordance with a photoinduced electron transfer mechanism.     

Preparation of nitrogen doped TiO2 photocatalyst by oxidation of titanium nitride with H2O2

Nitrogen doped anatase TiO₂ (N-TiO₂) were prepared by hydrothermally treating TiN with H₂O₂. The as-synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), UV-vis diffuse reflectance spectrum (DRS), Fourier transform infrared spectra (FT-IR) and X-ray photoelectron spectroscopy (XPS) techniques. The results confirmed that the hydrothermal oxidation is an effective method to prepare N-doped TiO₂ anatase. The nitrogen concentration in TiO₂ could be controlled by the concentration of H₂O₂ solution. Photocatalytic degradation of methyl orange (MO) was carried out under visible light and UV-visible light irradiation, respectively. The as-prepared optimal N-TiO₂ showed higher photocatalytic activity than N-P25 and P25, and exhibited excellent reusability.     

Preparation of boron-doped TiO2 films by autoclaved-sol method at low temperature and study on their photocatalytic activity

A series of uniform and transparent boron-doped TiO₂ films were synthesized from autoclaved-sol without organic solvent at low temperature. As-prepared B-TiO₂ films with two layers were characterized by XRD, DRS, XPS and AFM. The photocatalytic characteristics were measured based on the degradation of Rhodamine B (RhB) solution under visible or UV light. The results indicated that the anatase phase was the main crystal form of the films, containing a small amount of brookite. The presence of boron caused a red shift in the absorption band of TiO₂ films. The doped boron was mainly presented in the form of B₂O₃, O-Ti-B and O-Ti-B bonds, confirming that autoclaved-sol synthesis at low temperature allowed for incorporation of boron atoms into the TiO₂ matrix. Transmission of the films was about 90% in the visible region. The 10% (atom) B-TiO₂ film exhibited the best photocatalytic activity both in visible and UV light.     

Microwave assisted hydrothermal synthesis and characterization of ZnO–TNT composites

TiO₂ nanotubes with different contents of ZnO (3–40 wt.% ZnO) have been successfully synthesized by microwave assisted hydrothermal process by using commercial TiO₂-P25 as a precursor. The phase and crystallinity of the obtained ZnO–TNT were analyzed by X-ray Diffraction (XRD). The surface area of the ZnO–TNT was determined by BET method. The effect of the different contents of ZnO on morphology of TiO₂ nanotubes was investigated by SEM and TEM. Optical properties and band gap energy of ZnO–TNT were calculated by using UV–vis DRS spectroscopy and modified Kubelka–Munk equation. Photocatalytic performance of ZnO–TNT was investigated by degradation of rhodamine B (RhB) dye under UV and visible light irradiation. Increasing ZnO content in TNT gradually decreased the diameter and length of nanotubes. Furthermore, addition of 40 wt.% ZnO into the TNT exceeded the saturation limit of ion exchangeability of Zn²⁺ and Na⁺ ions and aggregation of finely dispersed ZnO particles on the surface of TNT were observed. The ZnO–TNT has shown relatively larger band gap energies than that of TiO₂-P25. However, ZnO–TNT has shown considerable increase in photo-activity for degradation of RhB dye in visible light as compared to UV light irradiation.     

Visible-light-responsive Ag–Si codoped anatase TiO2 photocatalyst with enhanced thermal stability

To utilize visible light more efficiently and enhance the photocatalytic performance of TiO₂, Ag–Si/TiO₂ photocatalyst was synthesized via a two-step method. The obtained materials were characterized by XRD, Raman, TEM, HRTEM, BET, TG–DTA, XPS, ICP as well as UV–vis DRS. All photocatalyst materials held an anatase phase confirmed by XRD, Raman and HRTEM. The Ag–Si/TiO₂ photocatalysts possessed high thermal stability and the phase transformation was retarded to about 900 °C revealed by XRD and TG–DTA. The Ag–Si/TiO₂ particles synthesized via the nonaqueous method were highly monodispersed and the particles size became smaller compared to the un-doped TiO₂, resulting in the enlargement of surface area. In addition, UV–vis light absorption shifted to visible region after Ag doping. XPS results demonstrated that Si weaved into the matrix of TiO₂ and enriched in the surface layer, while Ag dispersed on the surface of TiO₂ particles. The Ag dopant suppressed the recombination of photogenerated electrons and holes, Si enlarged the surface of photocatalysts. Silver and silicon co-doping improved the visible photocatalytic activity, which was evaluated by Rhodamine B (RhB) degradation. The photocatalytic activity of the obtained Ag–Si/TiO₂ sample was much more higher than those of pure TiO₂ and Ag/TiO₂, reaching the maximum at the Ag and Si content of 0.5 mol% and 20.0 mol%, respectively. The improved visible photocatalytic activity may be attributed to the synergetic effects of codoping by silver and silicon.     

Removal of fluoride from aqueous solution by polypyrrole/Fe3O4 magnetic nanocomposite

Highly efficient visible light TiO₂ photocatalyst was prepared by the sol-gel method at lower temperature (≤300 °C), and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and differential scanning calorimetry-thermogravimetric analysis (DSC-TGA). The effects of the heat treatment temperature and time of the as-prepared TiO₂ on its visible light photocatalytic activity were investigated by monitoring the degradation of methyl orange solution under visible light irradiation (wavelength ≥ 400 nm). Results show that the as-prepared TiO₂ nanoparticles possess an anatase phase and mesoporous structure with carbon self-doping and visible photosensitive organic groups. The visible light photocatalytic activity of the as-prepared TiO₂ is greatly higher than those of the commercial TiO₂ (P-25) and other visible photocatalysts reported in literature (such as PPy/TiO₂, P3HT/TiO₂, PANI/TiO₂, N-TiO₂ and Fe³⁺-TiO₂) and its photocatalytic stability is excellent. The reasons for improving the visible light photocatalytic activity of the as-prepared TiO₂ can be explained by carbon self-doping and a large amount of visible photosensitive groups existing in the as-prepared TiO₂. The apparent optical thickness (τ_app), local volumetric rate of photo absorption (LVRPA) and kinetic constant (k_T) of the photodegradation system were calculated.     

(N, F)-codoped TiO2 Nanocrystals as Visible Light-activated Photocatalyst

(N, F)-codoped anatase TiO₂ nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO₂ nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The (N, F)- codoped TiO₂ nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.     

Iron promotion of the TiO2 photosensitization process towards the photocatalytic oxidation of azo dyes under solar-simulated light irradiation

The photocatalytic oxidation of the azo dye Orange-II (Or-II) using Fe loaded TiO₂ (Fe–TiO₂) was studied under ultraviolet (UV), visible (vis) and simultaneous UV–vis irradiations using a solar light simulator. Photocatalysts were characterized by means of XRD, SEM-EDX, FTIR and DRS. Fe³⁺ species, identified in XPS analyses, were responsible of the increased absorption of visible light. Moreover, DRS analyses showed a decrease in the bandgap due to Fe³⁺ loading. Photocatalystic tests proved that Fe modification enhanced the TiO₂ photocatalytic activity towards Or-II photodegradation under simultaneous UV–vis irradiation. Even so, the performance of the Fe–TiO₂ samples towards the photodegradation of phenol, under UV irradiation, was lower than TiO₂ suggesting the recombination of the UV photogenerated electron–hole pair. Therefore, results evidence a Fe³⁺ promotion of the electron caption in the photosensitization process of TiO₂ by Or-II acting as a sensitizer. Such process leads to the Or-II photooxidation under UV–vis irradiation by losing energy in electron transferring processes to sensitize TiO₂, and, the formation of reactive oxygen species promoted by the injected electron to the TiO₂ conduction band.     

Photocatalytic degradation and mineralization of dye pollutants from wastewater under visible light using synthetic CuO-VO2/TiO2 nanotubes/nanosheets

CuO-VO₂/TiO₂ as a new nanocomposite was synthesized through hydrothermal method and identified by various spectroscopic techniques including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray analysis (EDX), UV–visible, differential reflectance spectroscopy (DRS), and Mott–Schottky. The presence of nanotubes/nanosheets in the synthesized nanocomposite was confirmed by HR-TEM. The anatase and rutile crystalline forms of TiO₂ were detected by Raman spectroscopy and X-ray diffraction (XRD). XPS analysis confirmed the presence of CuO and VO₂ in the nanocomposite. The surface area and the band-gap energy of the nanocomposite were determined via N₂ adsorption–desorption analysis and DRS. The presence of a p–n junction between TiO₂ (n-type) and CuO/VO₂ (p-type) was confirmed by the Mott–Schottky analysis. The photocatalytic activity of the nanocomposite against methylene blue (MB), methyl orange (MO), and cango red (CR) was studied under visible-light irradiation. The times of degradation for the decomposition of the dyes were 10–25 min. The rate constants of degradation for MB, MO, and CR were calculated as 0.34, 0.090, and 0.155 min^?1, respectively. The catalyst was recovered four times. In addition, the mineralization of the dyes was investigated by chemical oxygen demand (COD). The reaction was performed in the presence of different radical scavengers, and the ·OH was found to be the predominantly active species in the photodegradation of the dyes.

     

UV and visible photodecomposition of organic pollutants over micro arc oxidized Ag-activated TiO2 nanocrystalline layers

Although titania is one of the most important metal oxide photocatalysts, its practical applications are to some extent limited by its relatively wide band gap. Doping TiO₂ by metallic species has been expressed as a promising solution to decrease its band gap energy and enhance its photocatalytic performance. In this research, we employed micro arc oxidation technique to grow Ag-doped TiO₂ porous layers where influence of the electrolyte composition and the applied voltage on the surface morphology, topography, phase structure, chemical composition, and optical properties was investigated for the first time. The photocatalytic efficiency of the layers was studied using different model materials namely methylene blue and 4-chlorophenol solutions as well as gaseous benzene. A porous morphology with a rough surface was revealed by the SEM and AFM techniques. The pore size varied depending on the voltage and the electrolyte concentration. Compositional studies, conducted by XRD and XPS methods, showed that the fabricated layers mainly consisted of anatase phases. A small amount of rutile phase was also detected at high voltages, i.e. 500 V. Considering the XRD patterns, the anatase average crystalline size was determined as 67.8 and 21.5 nm for the pure TiO₂ and silver doped TiO₂ layers, respectively. A red-shift was observed in the absorbance edge of the layers when Ag was introduced into the titania lattice giving rise to a visible-light response. Comparing photocatalytic reaction rate constants of pure and Ag-doped titania, the doped layers exhibited more favorable potential to decompose the pollutants in aqueous phase under ultraviolet and visible lights. Moreover, the doped layers were useful to decompose the pollutants in gaseous phase under ultraviolet light.     

Mn-doped TiO2 nanopowders with remarkable visible light photocatalytic activity

TiO₂ nanocrystalline powders with various Mn-doping levels were synthesized by the sol-gel process using tetrabutyl titanate and manganese nitrate as precursors. The crystal structure, morphology, doping concentration, optical absorption property, and elemental state of the obtained samples were analyzed. TEM results showed that the synthesized TiO₂ powders were anatase nanoparticles about 7 nm in size. EDX and XPS analyses proved the incorporation of Mn ions into the TiO₂ lattice. A remarkable red shift of the absorption edge was achievable by increased Mn content, leading to gigantically narrowed energy gap to permit absorption well into the infrared spectral region. The dramatic optical absorbance of the doped TiO₂ nanopowders in the visible spectral region led to strong photocatalytic activity under visible light illumination, which was observed by measuring the degradation of methylene blue. In contrast, little degradation was observed for the pure TiO₂ powder. The optimum Mn/Ti ratio was observed to be 0.2 at.% for photocatalytic applications.