Photocatalytic removal of nitrogen oxides from air on TiO<Subscript>2</Subscript> modified with bases and platinum

The efficiency of TiO₂ (Degussa P-25) modified with an alkaline admixture (urea, BaO), sulfuric acid, or platinum in the photocatalytic oxidation of NO (50 ppm) with a flowing 7% O₂ + N₂ mixture under UV irradiation in a flow reactor at room temperature and atmospheric pressure is reported. Because of the progressive blocking of active sites of the photocatalyst by the reaction products (NO₂, NO₃⁻), it is impossible to realize prolonged continuous removal of NO _x (NO + NO₂) from air without catalyst regeneration at elevated temperatures. The efficiency of the photocatalysts is characterized by specific photoadsorption capacity (SPC) calculated from the total amount of NO _x adsorbed during 2-h-long irradiation. Modification of TiO₂ with 5% BaO or 5% urea raises the SPC of the catalyst by a factor of 2–3. Presumably, this promoting effect is due to the basic properties of these dopants, which readily sorb NO₂ and NO₃⁻. A considerable favorable effect on SPC is also attained by adding 0.5% Pt to (5% BaO)/TiO₂. The SPC of the (0.5% Pt)/TiO₂ catalyst depends on the state of the platinum. The samples calcined in air at 500°C, which contain Pt⁺ and Pt²⁺, have an approximately 2 times higher SPC than unpromoted TiO₂ and ensure a much larger NO₂/NO ratio at the reactor outlet. Conversely, the samples reduced in an H₂ atmosphere at 200°C, whose platinum is in the Pt0 state, show a lower SPC than the initial TiO₂ and cause no significant change in the NO₂/NO ratio.     

Fluorinated Mesoporous Anatase TiO<Subscript>2</Subscript> Microspheres with High Surface and Enhanced Photocatalytic Activity for the Degradation of Methyl Orange

Highly crystalline mesoporous TiO₂ microspheres with areas up to 122 m²/g and tunable pore size have been prepared through a combined sol–gel and solvothermal processes. The concentration of NaF exhibits a great effect on the morphology, crystallinity, crystal size and photocatalytic activity of the TiO₂ microspheres. A higher NaF concentration results in an increase in the average crystal size and pore size, whereas whereas it caused a decrease in the specific surface areas. All fluorinated TiO₂ microspheres showed a higher photocatalytic activity than P25 and pure TiO₂ microspheres obtained in the absence of NaF due to the effect of surface fluorination on the photoactivity of TiO₂. The approach described in this study provides a simple method to synthesize the micrometer-sized hierarchical structure of mesoporous TiO₂ microspheres that are ready for practical applications such as environmental pollutants removal and solar cell because these high active materials can be easily separated.     

Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Synthesis,Characterization and Photocatalytic Application of TiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript> Nanocomposite Obtained Under Non-thermal Plasma Condition at Atmospheric Pressure

A plasma-assisted synthesis of TiO₂/SnO₂ nanocomposite is described. In this approach, a precursor containing a mixture of [TiCl₃ and SnCl₂] exposed to electric discharge was oxidized by plasma-generated reactive species (HO^·/H₂O = 2.85 eV/SHE). SnO₂ microstructures with a diameter of 10–40 µm were coated by thin layers TiO₂ nanorods with mean diameter of 6–8 nm. The obtained TiO₂/SnO₂ nanocomposite was characterized by transmission and scanning electron microscopy, X-ray diffraction and Fourier transform infrared. TiO₂/SnO₂ nanocomposite was found to be a promising new material for the photocatalytic discoloration of aqueous Remazol Brilliant Blue-R dye under daylight and UVA light sources, due to the combined effects of large specific surface area and heterojunction which efficiently separates the electron–hole pairs delaying the charge recombination. The leaching test indicated that the nanocomposite is stable easily reusable.     

Synthesis and characterization of radiation sensitive TiO<Subscript>2</Subscript>/monazite photocatalyst

A TiO₂/monazite photocatalyst was prepared by embedding TiO₂ nanoparticles into a monazite substrate surface. TiCl₄ hydrolysis/citric acid chelating procedure under acidic conditions were used to synthesize the nanophase TiO₂ particles. The anatase TiO₂/monazite photocatalyst surface area, morphology, crystalline and elemental concentrations were characterized using Brunauer-Emmett-Teller (BET) method, scanning electron microscopy (SEM), X-ray diffraction (XRD), and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Monazite contains a large amount of Ce-, La-, Nd- and Th-PO₄ compounds; it has been known as a natural mineral material with minor radioactivity. TiO₂-CeO₂ composite is a kind of radiation sensitive photocatalyst in which the radiations of thorium nuclides give energy to trigger TiO₂ and cerium ions which play an energy absorber with charge separator. The result showed that methylene blue and phenol were spontaneously photocatalytic decomposed by TiO₂/monazite composite even in a dark environment. A synergistic effect was also examined with applied exterior UV or ⁶⁰Co irradiation. A hybrid mechanism is proposed; according by the radioluminescence (RL) from excited Ce ion by γ-radiation soliciting CeO₂/TiO₂ heterojunction (HJ). This seems to be a possible mechanism to explain this self-activated photo-catalytic behavior.     

Influence of MnO<Subscript>2</Subscript> on the photocatalytic activity of P-25 TiO<Subscript>2</Subscript> in the degradation of methyl orange

Influences of α-MnO₂, β-MnO₂, and δ-MnO₂ on the photocatalytic activity of Degussa P-25 TiO₂ have been investigated through the photocatalytic degradation of methyl orange. The TiO₂ photocatalyst, before and after being contaminated by MnO₂, was characterized by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). The results showed that photocatalytic activity of TiO₂ could be inhibited significantly or completely deactivated due to the presence of even a small amount of MnO₂ particles. It was found that the poisoning effect varied with the crystal phases of MnO₂ and the effect was in the order δ-MnO₂ >α-MnO₂ >β-MnO₂. The poisoning effect was attributed to the formation of heterojunctions between MnO₂ and TiO₂ particles. The heterojunctions changed the chemical state of Ti⁴⁺ and O²⁻ sites in the crystalline phase of TiO₂. MnO₂ in contact with TiO₂ particles also broadens the band-gap of TiO₂, which decreases UV absorption of TiO₂. It can also create some deep impurity energy levels serving as photoelectron-photohole recombination center, which accelerates the electron-hole recombination. Supported by the National Natural Science Foundation of China (Grant No. 20477009) and the Natural Science Foundation of Hebei Province (Grant No. E2005000183)     

Synthesis and thermal decomposition of neodymium(III) peroxotitanate to Nd<Subscript>2</Subscript>TiO<Subscript>5</Subscript>

Neodymium(III) peroxotitanate is used as a precursor for obtaining Nd₂TiO₅. The last one possesses numerous valuable electrophysical properties. TiCl₄, Nd(NO₃)₃·6H₂O and H₂O₂ in mol ratio 1:2:10 were used as starting materials. The reaction ambience was alkalized to pH = 9 with a solution of NH₃. The obtained neodymium(III) peroxotitanate and intermediate compounds of the isothermal heating were proved by the help of quantitative analysis and infrared spectroscopy (IRS). It has Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O composition. The absorption band observed in IRS at 831 cm^?1 relates to a triangular bonding of the peroxo group of Ti, at 1062 cm^?1—terminal groups Ti–OH and at 1491 and 1384 cm^?1—the bridging OH^?-groups Ti–O(H)–Ti. Nd₂TiO₅ was obtained by thermal decomposition of neodymium(III) peroxotitanate. The isothermal conditions for decomposition were determined on the base of differential thermal analysis, thermogravimetric and differential scanning calorimetry results in the temperature range of 20–1000 °C. The mechanism of thermal decomposition of Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O to Nd₂TiO₅ was studied. In the temperature range of 20–208 °C, a simultaneous decomposition of the peroxo groups by the separation of oxygen and hydrate water is conducted and Nd₄[Ti₂O₄(OH)₁₂] is obtained. From 208 to 390 °C, the terminal OH^?-groups are separated and Nd₄[Ti₂O₇(OH)₆] is formed. In the range of 390–824 °C, the bridging OH^?-groups are completely decomposed to Nd₂TiO₅. The optimal conditions for obtaining nanocrystalline Nd₂TiO₅ are 900 °C for 6 h and 20–80 nm.     

Rapid Synthesis of Mesoporous TiO2 for the Photoanodes in Dye Sensitized Solar Cells

Mesoporous TiO₂ microspheres with high specific surface areas were synthesized by means of a facile one‐step microwave hydrothermal process without using any template. The mesoporous materials were rapidly achieved using TiCl₄, urea and ammonium sulphate at comparatively low microwave power (400 W) for 8 min irradiation. The morphology and microstructure of the as‐prepared products were characterized by field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), transmission electron microscopy (TEM) and Brunauer‐Emmett‐Teller (BET) surface area analysis. Structural characterization indicates that the TiO₂ microspheres display mesoporous structure. The average pore sizes and BET surface areas of the spheres were 5.3 nm and 222 m²g^?1, respectively. The mesoporous nanocrystals synthesized at 160 °C for 8 min were then used to prepare the photoanode for dye sensitized solar cells (DSSCs). A high power conversion efficiency of 5.72% was achieved from the mesoporous TiO₂ based photoanode, representing about 25.7% improvement over the efficiency of P25 photoanode.     

Catalytic Properties of TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles in Plasma Chemical Treatment

We proposed here a new process coupling dielectric barrier discharge (DBD) plasma with magnetic photocatalytic material nanoparticles for improving yield in DBD degradation of methyl orange (MO). TiO₂ doped Fe₃O₄ (TiO₂/Fe₃O₄) was prepared by the sol-gel method and used as a new type of magnetic photocatalyst in DBD system. It was found that the introduction of TiO₂/Fe₃O₄ in DBD system could effectively make use of the energy generated in DBD process and improve hydroxyl radical contributed by the main surface Fenton reaction, photocatalytic reaction and catalytic decomposition of dissolved ozone. Most part of MO (88%) was degraded during 30 min at peak voltage of 13 kV and TiO₂/Fe₃O₄ load of 100 mg/L, with a rate constant of 0.0731 min^?1 and a degradation yield of 7.23 g/(kW h). The coupled system showed higher degradation efficiency for MO removal.     

Preparation of nanocrystalline Fe-doped TiO<Subscript>2</Subscript> powders as a visible-light-responsive photocatalyst

Nanocrystalline Fe-doped TiO₂ powders were prepared using TiOSO₄, urea, and Fe(NO₃)₃ · 9H₂O as precursors through a hydrothermal method. The as-synthesized yellowish-colored powders are composed of anatase TiO₂, identified by X-ray diffraction (XRD). The grain size ranged from 9.7 to 12.1 nm, calculated by Scherrer’s method. The specific surface area ranged from 141 to 170 m²/g, obtained by the Brunauer–Emmett–Teller (BET) method. The transmission electron microscopy (TEM) micrograph of the sample shows that the diameter of the grains is uniformly distributed at about 10 nm, which is consistent with that calculated by Scherrer’s method. Fe³⁺ and Fe²⁺ have been detected on the surface of TiO₂ powders by X-ray photoelectron spectroscopy (XPS). The UV–Vis diffuse reflection spectra indicate that the light absorption thresholds of the Fe-doped TiO₂ powders have been red-shifted into the visible light region. The photocatalytic activity of the Fe-doped TiO₂ was evaluated through the degradation of methylene blue (MB) under visible light irradiation. The Fe-doped TiO₂ powders have shown good visible-light photocatalytic activities and the maximum degradation ratio is achieved within 4.5 h.     

Synthesis and electrorheological characteristics of sea urchin-like TiO<Subscript>2</Subscript> hollow spheres

TiO₂ hollow microspheres with sea urchin-like hierarchical architectures were synthesized by a simple hydrothermal method. The as-synthesized hollow microspheres with hierarchical architectures consisting of many rhombic building units exhibit high specific surface area. Electrorheological (ER) properties of hierarchical hollow TiO₂-based suspension were investigated under steady and oscillatory shear. The hollow TiO₂-based suspensions show much higher yield stress and elasticity than pure TiO₂ suspension at the same electric field strength. This phenomenon was elucidated well in view of their dielectric spectra analysis. The sea urchin-like architectures result in stronger interfacial polarization of hollow TiO₂ suspension upon an electric field, showing higher ER activity. Also, hollow interiors of TiO₂ particles increase the long-term stability of suspensions and further merit the ER effect.     

Direct fabrication of anatase TiO<Subscript>2</Subscript> hollow microspheres for applications in photocatalytic hydrogen evolution and lithium storage

Hollow titanium dioxide (TiO₂) microspheres were synthesized in one step by employing tetrabutyl orthotitanate (TBOT) as a precursor through a facile solvothermal method in the presence of NH₄HCO₃. XRD analysis indicated that anatase TiO₂ can be obtained directly without further annealing. TiO₂ hollow microspheres with diameters in the range of 1.0–4.0 μm were confirmed through SEM and TEM measurements. The specific surface area was measured to be 180 m² g^?1 according to the nitrogen adsorption–desorption isotherms. Superior photocatalytic performance and good lithium storage properties were achieved for resultant TiO₂ samples. The H₂ evolution rate of the optimal sample is about 0.66 mmol h^?1 after loaded with 1 wt.% Pt (20 mg samples). The reversible capacity remained 143 mAh g^?1 at a specific current of 300 mA g^?1 after 100 charge–discharge cycles. This work provides a facile strategy for the preparation of hollow titanium dioxide microspheres and demonstrates their promising photocatalytic H₂ evolution and the lithium storage properties.

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Graphical abstract Hollow titanium dioxide spheres are directly synthesized via a facile template-free solvothermal method with the presence of NH₄HCO₃ based on inside-out Ostwald ripening (see picture), and demonstrated both as a photocatalyst for water splitting and a promising anode material for lithium-ion batteries. Superior photocatalytic performance and excellent lithium storage properties are achieved for resultant TiO₂ hollow microspheres.

     

Preparation of TiO<Subscript>2</Subscript>/activated carbon with Fe ions doping photocatalyst and its application to photocatalytic degradation of reactive brilliant red K2G

Titanium dioxide coated on activated carbon (AC) with Fe ions doping (Fe-TiO₂/AC) composite was prepared by an improved sol-gel method. The photocatalytic activities were tested by photocatalytic degradation of reactive brilliant red K2G in solution. The results show that in comparison with the agglomeration of pure TiO₂, the TiO₂ nanoparticles are well dispersed in the AC matrix, of which sizes are decreased with Fe ions doping. Additionally, the iron species on TiO₂ of composite are Fe₂O₃ and FeO, which do not affect the crystalline structures of TiO₂ nanoparticles. The AC matrix and iron doping content influence the fluorescence intensity of composite due to their effects on recombination probability of hole-electron pairs. Compared with TiO₂, 0.3% Fe-TiO₂, TiO₂/AC, 0.5% Fe-TiO₂/AC and 0.1% Fe-TiO₂/AC, the 0.3% Fe-TiO₂/AC shows the highest photoactivity with the complete mineralization of K2G for finite time due to the optimum Fe ions content and AC matrix. Furthermore, the kinetic constant (k = 0.0229 min⁻¹) of 0.3% Fe-TiO₂/AC composite is more than the sum of both TiO₂/AC (0.0154 min⁻¹) and 0.3% Fe-TiO₂ (0.0057 min⁻¹) because coexistence of the AC and Fe ions has an enlarging effect on improving the photoactivity of TiO₂. Supported by the Education Department Foundation of Hunan Province (Grant No. 08B063) and Science and Natural Science Foundation of Hunan Province (Grant No. 09JJ6101)     

Preparation and photoelectrochemical performance of TiO<Subscript>2</Subscript>/Ag<Subscript>2</Subscript>Se interface composite film

Coupling TiO₂ with a narrow band gap semiconductor acting as the photosensitizer has attracted much attention in solar energy exploitation. In this work, the porous TiO₂ film was first formed on the conducting glass plate (CGP) substrate by the decomposition of polyethylene glycol (PEG) mixing in titanium hydroxide sol at 450°C. Then, the TiO₂/Ag²Se interface composite film was fabricated by interface reaction of AgNO₃ with NaSeSO₃ on the activated surface of porous TiO₂ film. The results of SEM and XRD analyses indicated that the porous TiO₂ layer was made up of the anatase crystal, and the Ag₂Se layer was made up of congregative small particles that have low-temperature α-phase structure. Due to its efficient charge separation for the photo-induced electron-hole pairs, the TiO₂/Ag₂Se interface composite film as-prepared has good photovoltaic property and high photocurrent response for visible light, which have been confirmed by the photoelectrochemical measurements.     

Synthesis and photocatalytic activity assessing of the TiO<Subscript>2</Subscript> nanocomposites modified by some lanthanide ions and tin-derivative sandwich-type polyoxometalates

New nanocomposites containing sandwich-type polyoxometalate of [(PW₉O₃₄)₂(HOSn^IVOH)₃]^12? (P₂W₁₈Sn₃) loaded onto Ln-doped TiO₂ (Nd, Sm, Dy, Tb) nanoparticles were synthesized and their catalytic activities were assessed. The Ln–TiO₂ nanoparticles and Ln–TiO₂/P₂W₁₈Sn₃ nanocomposites were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction, field emission scanning electron microscope, energy dispersive analysis of X-rays spectra and diffuse reflectance spectra. The photocatalytic efficiency of the Ln–TiO₂ and Ln–TiO₂/P₂W₁₈Sn₃ were examined in the photodegradation of methyl orange and methylene blue solutions. It was revealed through different characterization techniques that the P₂W₁₈Sn₃ was successfully loaded on the lanthanide-doped anatase phase TiO₂ nanoparticles and the particles diameter were relatively 20–30 nanometers. It was revealed that doping by the lanthanide ions followed by loading of polyoxometalates improves the photocatalytic performance of TiO₂ effectively. The effects of operational parameters and the kinetics of photocatalytic degradation under UV light were discussed. The prepared nanocomposites were stable and could be easily separated from the reaction system.     

Dielectric properties and I-V characteristics of (Pb<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>)TiO<Subscript>3</Subscript> thin films improved by TiO<Subscript>2</Subscript> buffer layers

A TiO₂ thin buffer layer was introduced between the (Pb_0.4Sr_0.6)TiO₃ (PST) film and the Pt/Ti/SiO₂/Si substrate in an attempt to improve their electrical properties. Both TiO₂ and PST layers were prepared by a chemical solution deposition method. It was found that the TiO₂ buffer layer increased the (100)/(001) preferred orientation of PST and decreased the surface roughness of the films, leading to an enhancement in electrical properties including an increase in dielectric constant and in its tunability by DC voltage, as well as a decrease in dielectric loss and leakage current density. At an optimized thickness of the TiO₂ buffer layer deposited using 0.02 mol/l TiO₂ sol, the 330-nm-thick PST films had a dielectric constant, loss and tunability of 1126, 0.044 and 60.7% at 10 kHz, respectively, while the leakage current density was 1.95 × 10⁻⁶ A/cm² at 100 kV/cm.     

Study of Fe-doped V<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript> catalyst for an enhanced NH<Subscript>3</Subscript>-SCR in diesel exhaust aftertreatment

Selective catalytic reduction (SCR) with ammonia has been considered as the most promising technology, as its effect deals with the NO_X. Novel Fe-doped V₂O₅/TiO₂ catalysts were prepared by sol–gel and impregnation methods. The effects of iron content and reaction temperature on the catalyst SCR reaction activity were explored by a test device, the results of which revealed that catalysts could exhibit the best catalytic activity when the iron mass ratio was 0.05%. It further proved that the VTiFe (0.05%) catalyst performed the best in denitration and its NO_X conversion reached 99.5% at 270 °C. The outcome of experimental procedures: Brunauer–Emmett–Teller surface area, X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and adsorption (H₂-TPR, NH₃-TPD) techniques showed that the iron existed in the form of Fe³⁺ and Fe²⁺ and the superior catalytic performance was attributed to the highly dispersed active species, lots of surface acid sites and absorbed oxygen. The modified Fe-doped catalysts do not only have terrific SCR activities, but also a rather broad range of active temperature which also enhances the resistance to SO₂ and H₂O.     

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.     

Kinetic studies of direct blue photodegradation over flower-like TiO<Subscript>2</Subscript>

The kinetics of photocatalytic oxidation reaction for direct blue solution was studied by using flower-like TiO₂ under the irradiation of ultraviolet (UV) light. A series of possible affecting factors were studied, including pH value, the additive amount of light catalyst, H₂O₂ and with or without Ag modification. The kinetics of photocatalytic degradation under UV was found following a pseudo-second-order reaction kinetic model with high regression coefficients (R ²). It has been demonstrated that the initial concentration and its related factors have influenced the photocatalytic degradation efficiency and corresponding kinetic parameters. Also, the kinetic parameter k is increasing with the degradation efficiency.     

Photoelectrochemical study of electrodeposited TiO<Subscript>2</Subscript> thin films onto F:SnO<Subscript>2</Subscript> substrates

TiO₂ thin films have been effectively fused onto F:SnO₂ (FTO) substrates via the electrodeposition method. The influence of deposition temperature on the synthesis of F:SnO₂ substrates and relative information of as-deposited and annealed TiO₂ thin films have been studied. Novel TiO₂ microspheres are detected on F:SnO₂ substrates at an optimized electrodeposition potential. Raman bands approve the creation of single-anatase-phase TiO₂. The optimized deposition surroundings show a decrease in the band gap of F:SnO₂ substrates and TiO₂ thin films. The determined photoelectrochemical properties of annealed TiO₂ thin films indicate a fill factor of 51% and power conversion efficiency of 0.15% for application in solar cells.