Influence of transition metal-doped titanium(IV) dioxide on the photodegradation of polyethylene

The effects of adding dispersed powders of various forms of titanium(IV) dioxide on the photodegradation of polyethylene have been examined from the following points of view: effect of crystal form, concentration of pigment, transition metal ion, dopant concentration, calcination temperature of pigment, and pigment coating.The rate of photodegradation of polyethylene is reduced by adding certain grades of TiO₂ such as coated TiO₂ particles or TiO₂ doped with small percentages of Cr or Mn ions. The rate is increased on adding TiO₂ doped with V and especially Mo or W ions. The anatase form of TiO₂ is more photoactive than the rutile form, and the effect of increasing the calcination temperature of the pigment is to reduce photoactivity by boosting the rutile fraction. The concentration dependences of the degradation rates are complex, but can be directly related to the percentage of anatase achieved after calcination. Even the most aggressive of the metal-doped pigments are less photoactive than the Degussa P25 material, containing both rutile and anatase.     

The effects of trace elements on the crystal properties of TiO2

The effects of trace element doping of TiO₂ on the crystal growth and on the anatase-to-rutile phase transformation of TiO₂ were investigated. The co-precipitation process, from sulfate solution, of doped (Cr, Fe, V, Nb, Si, P) TiO₂ was also studied. The heating temperatures were 473, 673, 873, 993, 1133 K and a higher temperature needed to achieve a rutile content of 98–99%. Traces of reduced titanium were found in freshly calcined anatase by X-ray diffraction. Pure anatase structure was found in 85% of the samples heated below 1000 K. Anatase-to-rutile transformation was accelerated by the mmol% content of Nb, Cr, Si, and Fe in TiO₂. Interaction of co-precipitated or impregnated cations was found critical in the phase transformation process. Nb retarded the crystal growth during calcination. Sulfate ions minimized the specific surface area of TiO₂ heated at low temperatures. These results of doped TiO₂ serve to promote the development of new high-technology TiO₂ products for photocatalytic purposes.     

Preparation and Characterization of Bismuth Doped TiO2 Thin Films

A series of Bismuth-doped titanium oxide (Bi-doped TiO₂) thin films on glass substrates have been prepared by sol-gel dip coating process. The prepared catalysts were characterized by XRD and XPS. The photocatlytic activity of the thin film catalysts was evaluated through the photodegradation of aqueous methyl orange under UV illumination. The experiments demonstrated that the Bi-doped TiO₂ prepared was anatase phase. The doped bismuth was in the 3⁺ oxidation state. The presence of Bi significantly enhanced the photocatalytic activity of TiO₂ films. At calcination temperature of 500°C, with doping concentration of 2 wt %, Bi-doped TiO₂ thin film showed the highest photocatalyic activity.     

TiO2 Synthesis by the Pechini’s Method and Application for Diclofenac Photodegradation†

In this work, the effect of the calcination temperature on the TiO₂ synthesis using Pechini’s method was reported. The adopted calcination temperatures were 500, 600, and 700°C. XRD measurements indicated the composition of crystalline phases, and from there, the conversion of the anatase phase to rutile. TiO₂ Evonik^® was used as a reference standard and sodium diclofenac as a standard for photodegradation assessment. The average crystalline size increased. In both cases, this trend accompanied the increase in calcination temperature. The optical properties were performed using diffuse UV‐Vis reflectance. Results obtained indicated maximum absorption wavelength values more intense and displaced to the visible region. Also, the estimated band gap energy values decreased. The photocatalytic performance of TiO₂ samples was superior to the reference catalyst (TiO₂ Evonik^®). Especially in the first 10 minutes, the comparative photodegradation was up to approximately 58% higher. The photodegradation kinetic constants were also higher, and by comparison, up to approximately 73% higher. Toxicity measurements, using Artemias salina, also indicated similar decay behavior in the first 10 minutes, with a performance of up to approximately 60%.     

High temperature stability and photocatalytic activity of nanocrystalline anatase powders with Zr and Si co-dopants

TiO₂ nanopowders doped by Si and Zr were prepared by sol–gel method. The effects of Si and Zr doping on the structural, optical, and photo-catalytic properties of titania nanopowders have been studied by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a significant effect on anatase phase stability, crystallinity, and particle size of TiO₂. Titania rutile phase formation in ternary system (Ti–Si–Zr) was inhibited by Zr⁴⁺ and Si⁴⁺ co-doped TiO₂ in high temperatures (500–900 °C) and 36 mol% anatase composition is retained even after calcination at 1,000 °C. The photocatalyst activity was evaluated by photocatalytic degradation kinetics of aqueous methylen orange under visible radiation. The results show that the photocatalytic activity of the 20 %Si and 15 %Zr co-doped TiO₂ nanopowders have a larger degradation efficiency than pure TiO₂ under visible light.     

Photocatalytic Activity of N-doped TiO2 Photocatalysts Prepared from the Molecular Precursor (NH4)2TiO(C2O4)2

We developed a novel approach for the preparation of N-doped TiO₂ photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO₂ were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N₂ adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO₂ photocatalysts calcined below 700 oC are the pure anatase phase but that calcined at 700 oC is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO₂ which leads to the narrowing of bad gap of pure anatase N-TiO₂. Among all photocatalysts, N-TiO₂ photocatalysts calcined at 600 and 400 oC exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO₂ photocatalyst calcined at 700 oC exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.     

Transition metal-doped titanium(IV) dioxide: Characterisation and influence on photodegradation of poly(vinyl chloride)

The effects of transition metal dopants (V(IV), V(V), Mn(II), Cr(III), Mo(V), and W(V)), introduced into TiO₂, upon the rate of photodegradation of poly(vinyl chloride) (PVC) films containing TiO₂ have been measured. The rates were determined mainly by monitoring carbonyl group formation. In another set of experiments, the rates of chloride ion release from irradiated PVC particles suspended in water undergoing agitation with air or O₂ in the presence of particles of doped TiO₂ were measured electrochemically. The doping of TiO₂ (rutile) with Cr(III), V(V) or Mn(II) reduces the photoactivity of the pigment, while doping by Mo(V) or W(V) enhances its photoactivity; the results obtained from carbonyl index measurements are paralleled closely by those from chloride ion release. Even the most aggressive doped pigments were less reactive than Degussa P25 pigment, while the greatest protection to PVC film was offered by TiO₂ particles coated with Al₂O₃ or SiO₂. Overall, the photoactivity of doped TiO₂ is a complex function of dopant concentration, the energy levels of the dopants in the TiO₂ lattice, their d electronic configuration and their local distribution. Photoactivity is also linked to other factors such as crystal type, particle size distribution and surface area. There is a clear relationship between the tendency of the dopant to induce the rutile-to-anatase transition and its effect in enhancing the photoactivity of the pigment. The characterisation of the doped pigments was achieved using X-ray powder diffraction, EPR spectroscopy, diffuse reflectance UV-vis spectrophotometry, scanning optical and electron microscopy and particle size analysis using LALLS.     

Temperatures and kinetics of anatase to rutile transformation in doped TiO<Subscript>2</Subscript> heated in microwave field

The influence of aliovalent ions such as Mn, Cr, Fe, Mo, and V on the temperature and kinetics of anatase to rutile phase transformation in TiO₂ heated in microwave field was studied in this work. The results indicated that heat treatment method and dopants considerably affected the anatase-to-rutile phase transition temperature and kinetics of transformation. The activation energy for anatase to rutile transformation of TiO₂ derived from the isothermal data was found to be 328.4 kJ mol^–1, which was considerably reduced by the addition of dopants in TiO₂ matrix. The activation energy for Mo, Mn and V doped samples was 252.0, 101.3 and 96.4 kJ mol^–1, respectively.     

The Critical Effect of Niobium Doping on the Formation of Mesostructured TiO2: Single‐Crystalline Ordered Mesoporous Nb‐TiO2 and Plate‐like Nb‐TiO2 with Ordered Mesoscale Dimples

Highly ordered mesoporous niobium‐doped TiO₂ with a single‐crystalline framework was prepared by using silica colloidal crystals with ca. 30 nm in diameter as templates. The preparation of colloidal crystals composed of uniform silica nanoparticles is a key to obtain highly ordered mesoporous Nb‐doped TiO₂. The XPS measurements of Nb‐doped TiO₂ showed the presence of Nb⁵⁺ and correspondingly Ti³⁺. With the increase in the amount of doped Nb, the crystalline phase of the product was converted from rutile into anatase, and the lattice spacings of both rutile and anatase phases increased. Surprisingly, the increase in the amount of Nb led to the formation of plate‐like TiO₂ with dimpled surfaces on one side, which was directly replicated from the surfaces of the colloidal silica crystals.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Hydrothermal synthesis and enhanced photocatalytic activity of mixed-phase TiO2 powders with controllable anatase/rutile ratio

In this study, mixed-phase TiO₂ powders were novelly synthesized via a facile and mild hydrothermal method without any post-heat treatment. TiOSO₄ and peroxide titanic acid (PTA) were used as inorganic titanium sources, while no special solvent or additive were introduced. The XRD and TEM results showed the mixed-phase TiO₂ powders were composed of anatase and rutile phases, and the PTA sol played an important role on forming the rutile nucleus. The proportion of rutile in the mixed-phase TiO₂ could be easily controlled in the range of 0%–70.5% by changing the amount of PTA sol used in the synthesis process. The UV-Visible absorption spectra indicated the prepared mixed-phase TiO₂ showed enhanced visible light absorption with the increase of rutile ratio. The photodegradation experiments revealed the mixed-phase TiO₂ exhibited the best photocatalytic activity at the rutile ratio of 41.5%, while a higher or lower rutile ratio both resulted in the decrease of photocatalytic activity.     

Analysis of preparation of TiO<Subscript>2</Subscript> particles by diffusion flame reactor for photodegradation of phenol and toluene

TiO₂ nanoparticles were produced in the diffusion flame reactor, and the size and anatase/rutile content of TiO₂ were examined by a Particle Size Analyzer and X-ray diffraction, respectively. Increase in fuel/O₂ ratio, initial concentration of TiCl₄ or total gas flow rate causes the larger particle size and the higher rutile composition. The photocatalytic activities of TiO₂ powders were tested on the decompositions of phenol and toluene in the aqueous solution under UV irradiation. The degradation rate increases as the TiO₂ particle size decreases and as the initial concentration of phenol or toluene increases. The photodegradation rate of phenol by TiO₂ particles is higher than that of toluene at the same process conditions. The computational method was used to simulate the gas temperature, velocity and species mass fractions inside the diffusion flame reactor during synthesis of TiO₂ nanoparticles. The measured and simulated temperature results were compared on several positions above the burner and both of them show good agreements. The typical contours of TiCl₄, TiO₂ mass fractions and gas velocities in flame reactor were presented.     

Preparation and spectroscopic characterization of visible light sensitized N doped TiO2 (rutile)

Nitrogen doped TiO₂ represents one of the most promising material for photocatalitic degradation of environmental pollutants with visible light. However, at present, a great deal of activity is devoted to the anatase polymorph while few data about rutile are available. In the present paper we report an experimental characterization of N doped polycrystalline rutile TiO₂ prepared via sol-gel synthesis. Nitrogen doping does not affect the valence band to conduction band separation but, generates intra band gap localized states which are responsible of the on set of visible light absorption. The intra band gap states correspond to a nitrogen containing defect similar but not coincident with that recently reported for N doped anatase.     

Effect of heat treatment on the properties and structure of TiO2 nanotubes: phase composition and chemical composition

Titanium oxide (TiO₂) nanotubes prepared by electrolytic anodisation of a titanium electrode have been systematically heat treated to control the conversion of the as‐prepared amorphous structure to nanocrystalline anatase and rutile. Raman spectroscopy revealed that the temperature of calcination is critical in determining the structure and crystallinity of the titania. X‐ray Photoelectron Spectroscopy analysis shows the as‐prepared film to consist mainly of oxide, although a small amount of fluoride contamination remains from the electrolyte. Organic components from post‐anodising cleaning treatments were also present. Fluorine ions are gradually ejected from the anodic layer during annealing and the fluorine concentration is negligible in samples that are heat treated above 400 °C. Choosing the appropriate annealing temperature allows the structure to be made up of defined proportions of anatase and rutile with a reduced contamination of species from the electrolyte or organic solvents. Copyright © 2010 John Wiley & Sons, Ltd.     

Crystallization kinetics study of In-doped and (In-Cr) co-doped TiO2 nanopowders using in-situ high-temperature synchrotron radiation diffraction

The influence of TiO₂ nanopowder doping with 4 wt% indium and 2 wt% each of indium and chromium on phase transformation was studied. Samples were heated from ambient temperature to 950 °C in sealed quartz capillaries, and in-situ synchrotron radiation diffraction measurements were obtained. Capillary sealing yielded an increase in capillary gas pressure to 0.42 MPa at 950 °C in proportion to absolute temperature by Gay-Lussac’s Law. The initial synthesized samples were amorphous, and crystalline anatase appeared at 200 °C. Crystalline rutile appeared at 850 °C for the nanomaterials that were doped with In and In and Cr. A change in sealed-capillary oxygen partial pressure yielded a decrease and an increase in crystallization temperature, respectively, for the amorphous-to-anatase and anatase-to-rutile transformations. Crystalline titania (anatase and rutile) formed from the amorphous titania by 800 °C and 900 °C, for materials doped with In and In-Cr, respectively. The anatase concentration that was dominant in the In-doped materials up to 950 °C and the higher rutile concentration for the In-Cr doped materials from 900 to 950 °C results from the defect structure that was induced by doping. Cr-ions in the Ti sub-lattice retarded the transformation of anatase to rutile when compared with the retarding effect of mixed In/Cr ions. The transformation results because of the relatively smaller radius of Cr-ions when compared with the In-ions. The differences in phase-transformation kinetics for In, In-Cr and for undoped nanopowders in the literature agree with the calculated transformation activation energies.     

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

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

Effect of crystal form and particle size of titanium dioxide on the photodegradation behaviour of ethylene-vinyl acetate copolymer/low density polyethylene composite

The photodegradation behaviour of ethylene-vinyl acetate copolymer (EVA)/low density polyethylene (LDPE) composite containing four different types of titanium dioxide (TiO₂) was investigated through colour difference, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and mechanical tests. The results showed that the performance losses of composites were qualitatively correlated with the degradation degree. The vinyl acetate (VA) groups in EVA were sensitive to UV light and the photodegradation mainly occurred in the amorphous region. The chain scission and annealing effect facilitated the secondary crystallization of composites. The heterogeneous nucleation effect of TiO₂ on the crystallization of composites was related to the particle size of TiO₂. The micro rutile TiO₂, micro anatase TiO₂ and their mixture (rutile/anatase = 13/87) exhibited a photo-stabilising effect, while the nano mixed crystals TiO₂ (rutile/anatase = 20/80) had an opposite effect.     

F and Fe co-doped TiO2 with enhanced visible light photocatalytic activity

Four different sols, pure TiO₂, F doped TiO₂, Fe doped TiO₂, and F–Fe co-doped TiO₂ sols, were prepared by peroxidation at low temperature. The crystal structure, morphology, light adsorption, and photocatalytic properties of the pure and doped TiO₂ were examined by X-ray diffraction, transmission electron microscopy, and ultraviolet–visible spectrophotometry. The relationship between the average size, crystal type, range of visible light absorption, and photocatalytic activity and content and type of doped ions were investigated. The results showed that the average size of the F–Fe co-doped TiO₂ composed of both the anatase and rutile phases was the same as that of pure TiO₂. Furthermore, the visible light photocatalytic activity of the F–Fe co-doped TiO₂ was significantly improved over pure TiO₂, F-doped TiO₂, and Fe-doped TiO₂ due to the large red shift in the light adsorption edge.     

Two‐Dimensional Hollow TiO2 Nanoplates with Enhanced Photocatalytic Activity

Two‐dimensional anatase TiO₂ hollow nanoplates were firstly synthesized through a facile synthesis route by using α‐Fe₂O₃ nanoplates as removable templates. Two‐dimensional hollow TiO₂ nanoplates with different ratios of anatase and rutile phases were obtained by adjusting the calcining temperature. The average diameters were around 600 nm, and the shell thickness was approximately 30 nm. The photocatalytic performance of TiO₂ was investigated by decomposing rhodamine B under simulated sunlight. Among the TiO₂ samples, the anatase TiO₂ hollow nanoplates manifested a significant enhancement in the photocatalytic performances. The excellent catalytic performance can be attributed to the unique structure of the two‐dimensional anatase TiO₂ hollow nanoplates, including a large surface area and increased dye–photocatalyst contact areas as well as more active sites for photodegradation.     

氮掺杂纳米多孔TiO2∶EDTA-Na2辅助水热合成及光催化性能

利用螯合剂乙二胺四乙酸二钠(EDTA-Na₂)作为致孔剂,以三氯化钛(TiCl₃)为前驱体,利用水热法直接合成了氮掺杂的纳米多孔TiO₂。通过 SEM、XRD、IR、低温N2吸附-脱附、XPS、热重分析(TG)和紫外可见(UV)光谱对样品进行了表征与分析。结果表明所合成TiO₂以锐钛矿相形式存在,氮掺在TiO₂晶面之间,具有典型的介孔结构和较高的比表面积,通过改变EDTA-Na₂的浓度,比表面积可控制在95~216 m²·g^-1之间。这种纳米多孔TiO₂在光降解甲基橙的实验中表现出很好的光催化活性,且随着EDTA-Na₂的浓度增大而逐渐增加。