Solar-light-induced photocatalytic decomposition of two azo dyes on new TiO2 photocatalyst containing nitrogen

The photocatalytic decolourisation of two azo dyes—Reactive Red 198 and Direct Green 99—in an aqueous solution by the artificial visible light radiation was investigated. The industrial metatitanic acid (H₂TiO₃) obtained directly from the sulphate technology installation was N-doped and used as photocatalyst. H₂TiO₃ was calcinated at different temperatures, ranging from 300 to 500 °C, for 4 or 20 h, respectively, in an ammonia atmosphere. The UV–vis/DR spectra of the modified catalysts exhibited an additional maximum in the vis region (λ ≈ 476.8 nm, E_G = 2.60 eV for catalysts calcinated for 4 h and λ ≈ 479.5 nm, E_G = 2.59 eV for catalysts calcinated for 20 h, which may be due to the presence of nitrogen in TiO₂ particles. The chemical structure of the modified photocatalysts was investigated using FTIR/DRS spectroscopy and the presence of nitrogen was confirmed. A photocatalytic activity of the investigated catalysts was determined on the basis of a decomposition rate of azo dyes. The decomposition of Reactive Red 99 increased with increasing the calcination temperature of photocatalysts, whereas the activity of the prepared photocatalysts towards Direct Green 198 degradation was as follows: 300–20 h < 400–20 h < 500–20 h < 300–4h < 400–4 h < 500–4 h. Both, the calcination time and temperature had no influence on the amount of nitrogen-doped into TiO₂ structure. The inversely proportional linear dependence between the decomposition rates of azo dyes and the intensity of the band attributed to the hydroxyl groups for both dissociated water and molecularly adsorbed water was observed. With increasing temperature of calcinations, the amount of the hydroxyl groups decreased, whereas the decomposition of azo dyes increased.     

Preparation,characterization and photocatalytic activity evaluation of micro- and mesoporous TiO2/spherical activated carbon

The influences of heat-treatment temperature and activation time on the properties of TiO₂ supported on spherical activated carbon (TiO₂/SAC) were investigated. Nano-sized TiO₂ was dispersed on the spherical activated carbon with the size of 10–30 nm. Some anatase phase of TiO₂ was transformed to rutile phase of TiO₂ with an increase of heat-treatment temperature. All of the TiO₂/SAC photocatalysts had microporous structure, with the mesopore volume increasing over an activation time of 6 h. The TiO₂/SAC photocatalysts obtained at activation times of 6 h and 9 h were observed synergistic effects between adsorption and photocatalysis in the removal of humic acid.     

A novel TiO2 − xNx/BN composite photocatalyst: Synthesis,characterization and enhanced photocatalytic activity for Rhodamine B degradation under visible light

A novel TiO_2 − xN_x/BN composite photocatalyst was prepared via a facile method using melamine–boron acid adducts (M·2B) and tetrabutyl titanate as reactants. The morphological results confirmed that nitrogen-doped TiO₂ nanoparticles were uniformly coated on the surface of porous BN fibers. A red shift of absorption edge from 400 nm (pure TiO₂) to 520 nm (TiO_2 − xN_x/BN composites) was observed in their UV–Vis light absorption spectra. The TiO_2 − xN_x/BN photocatalysts exhibited enhanced photocatalytic activity for the degradation of Rhodamine B (RhB) and the highest photocatalytic degradation efficiency reached 97.8% under visible light irradiation for 40 min. The mechanism of enhanced photocatalytic activity was finally proposed.     

Decomposition of nonionic surfactant on a nitrogen-doped photocatalyst under visible-light irradiation

A visible-light-active N-containing TiO₂ photocatalysts were prepared from crude amorphous titanium dioxide by heating amorphous TiO₂ in gaseous NH₃ atmosphere. The calcination temperatures ranged from 200 to 1000 °C, respectively. UV–vis/DR spectra indicated that the N-doped catalysts prepared at temperatures <400 °C absorbed only UV light (E_g = 3.3 eV), whereas samples prepared at temperatures ≥400 °C absorbed both, UV (E_g = 3.10–3.31 eV) and vis (E_g = 2.54–2.66 eV) light. The chemical structure of the modified photocatalysts was investigated using FT-IR/DRS spectroscopy. All the spectra exhibited bands indicating nitrogen presence in the catalysts structure. The photocatalytic activity of the investigated catalysts was determined on a basis of a decomposition rate of nonionic surfactant (polyoxyethylenenonylphenol ether, Rokafenol N9). The most photoactive catalysts were those calcinated at 300, 500 and 600 °C. For the catalysts heated at temperatures of 500 and 600 °C Rokafenol N9 removal was equal to 61 and 60%, whereas TOC removal amounted to 40 and 35%, respectively. In case of the catalyst calcinated at 300 °C surfactant was degraded by 54% and TOC was removed by 35%. The phase composition of the most active photocatalysts was as follows: (a) catalyst calcinated at 300 °C—49.1% of amorphous TiO₂, 47.4% of anatase and 3.5% of rutile; (b) catalyst calcinated at 500 °C—7.1% of amorphous TiO₂, 89.4% of anatase and 3.5% of rutile; (c) catalyst calcinated at 600 °C—94.2% of anatase and 5.8% of rutile.     

Lithium-mediated ring opening of 1,4-dioxane and structural characterization of a Li12O12 truncated octahedron

The equimolar reaction of ^tBuLi with 4-Cl-2,6-Me₂-C₆H₂OH (ArOH) in 1,4-dioxane led to the unexpected formation of the mixed-anion, 1D polymer [(ArO)₂(RO)₄Li₆ · (diox)]_∞, 1 (where RO = H₂CC(H)OCH₂CH₂O⁻). Incorporation of the alkoxy vinyl ether is due to cleavage of 1,4-dioxane by ^tBuLi. Compound 1 can also be prepared rationally by the reaction of ⁿBuLi with ethylene glycol vinyl ether and ArOH in 1,4-dioxane solution. Direct lithiation of ethylene glycol vinyl ether results in the formation of the alkoxide [ROLi]₁₂, 2. The crystal structure of 2 reveals an unusual truncated octahedral arrangement in the solid state, where each metal is chelated by a vinyl ether subunit.     

SnS2/TiO2 nanocomposites with enhanced visible light-driven photoreduction of aqueous Cr(VI)

SnS₂/TiO₂ nanocomposites have been synthesized via microwave assisted hydrothermal treatment of tetrabutyl titanate in the presence of SnS₂ nanoplates in the solvent of ethanol at 160 °C for 1 h. The physical and chemical properties of SnS₂/TiO₂ were studied by XRD, FESEM, EDS, TEM, XPS and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activity of SnS₂/TiO₂ nanocomposites were evaluated by photoreduction of aqueous Cr(VI) under visible light (λ>420 nm) irradiation. The experimental results showed that the SnS₂/TiO₂ nanocomposites exhibited excellent reduction efficiency of Cr(VI) (~87%) than that of pure TiO₂ and SnS₂. The SnS₂/TiO₂ nanocomposites were expected to be a promising candidate as effective photocatalysts in the treatment of Cr(VI) wastewater.     

Coagulation of bentonite suspension by polyelectrolytes or ferric chloride: Floc breakage and reformation

Coagulation process usually involves different hydrodynamic conditions, in particular when it is followed by a filtration step. In this study, coagulation performance was investigated under a wide range of shear stress. Floc behaviour was followed in-line by laser granulometry to determine size distribution and structure. Synthetic suspension of bentonite in tap water was used as a reference for mineral solids in surface water. Three cationic polymers (polyamine based and polyDADMAC) and ferric chloride were tested using different coagulation reactor geometries. Jar-test indicated coagulation performance under mild hydrodynamic conditions and Taylor–Couette reactors were used to create shear stresses up to 8 Pa. Flocs formed with ferric chloride are not able to grow under middle shear stress like 1.5 Pa. On the contrary, polyelectrolytes lead to large flocs, dense (D_f = 2.6) and resistant to shear stress. A qualitative comparison of floc resistance to shear depending on hydrodynamic conditions and coagulant type is given through the calculation of the strength factor. Fractal dimension measurements indicate a mechanism of particle erosion when flocs are subjected to a higher shear stress in Taylor–Couette reactor. Floc re-growth is also investigated, and breakage appears to be non-reversible regardless of coagulant and conditions experimented.     

Preparation of a composite coagulant: Polymeric aluminum ferric sulfate (PAFS) for wastewater treatment

A new composite coagulant polymeric aluminum ferric was synthesized and parameters affecting the coagulant performance such as reaction temperature and time, and OH/Fe, P/Fe and Al/Fe molar ratios in this study, were examined. In addition, to obtain the optimum synthetic conditions resulting in the maximum turbidity removal efficiency, response surface methodology (RSM) was used to assess their interactive effects on coagulation–flocculation performance. The results showed that reaction temperature (60–80 °C) and time (30–50 min), and OH/Fe (0.1–0.3), P/Fe (0.2–0.3) and Al/Fe (1:9–1:10) molar ratios were favorable to the preparation process. The optimum synthesis conditions were reaction temperature and time, and OH/Fe, P/Fe and Al/Fe molar ratios of 80 °C, 40 min, 0.1, 0.25 and 1:10, respectively. Evaluation of the coagulation–flocculation process showed that COD (chemical oxygen demand) and turbidity removal efficiency of 82.8% and 98.2%, respectively, were achieved at coagulant dosage of 45 mg/L, wastewater initial pH of 8.5, and rapid agitation speed of 250 rpm. In addition, charge neutralization and adsorption/bridging coagulation–flocculation mechanisms played an important role in reducing the surface charge of colloids.     

The effects of solvents on the formation of sol–gel-derived Bi12SiO20 thin films

The sol–gel method was used to synthesize Bi₁₂SiO₂₀ thin films. Two synthesis routes with two different solvents, i.e., 2-ethoxyethanol and acetic acid, were used and compared. Thin films were deposited onto Pt/TiO₂/SiO₂/Si substrates by spin-coating at 3000 rpm and annealed at 700 °C for 1 h. A different coordination of the bismuth ion was observed in the sols prepared with acetic acid (AcOH), and as a result, stable sols were formed with a shorter gelation time t_G = 84 h (c = 0.76 M), when compared with the sols prepared from 2-ethoxyethanol (EtoEtOH) t_G = 580 h (c = 0.76 M). The microstructures of the Bi₁₂SiO₂₀ thin films prepared from sols using EtoEtOH were homogeneous and dense. On the other hand, a porous microstructure was observed for the Bi₁₂SiO₂₀ thin films deposited from the sol in which AcOH was used as the solvent.     

Low temperature sintering and microwave dielectric properties of TiO2 ceramics

The TiO₂ ceramics were prepared by a solid-state reaction in the temperature range of 920–1100 °C for 2 h and 5 h using TiO₂ nano-particles (Degussa-P25 TiO₂) as the starting materials. The sinterability and microwave properties of the TiO₂ ceramics as a function of the sintering temperature were studied. It was demonstrated that the rutile phase TiO₂ ceramics with good compactness could be readily synthesized from the Degussa-P25 TiO₂ powder in the temperature range of 920–1100 °C without the addition of any glasses. Moreover, the TiO₂ ceramics sintered at 1100 °C/2 h and 920 °C/5 h demonstrated excellent microwave dielectric properties, such as permittivity (Ɛ_r) value >100, Q × f  > 23,000 GHz and τ_f ≅ 200 ppm/°C.     

Preparation of dye sensitized solar cell by using supercritical carbon dioxide drying

Dye-sensitized solar cells (DSSC) derived from TiO₂ aerogel film electrodes were fabricated. TiO₂ aerogels were obtained by using sol–gel method and supercritical carbon dioxide (sc-CO₂) drying. First, TiO₂ wet gels were obtained by sol-gel method. Then, the solvents in the TiO₂ wet gels were replaced by acetone. The TiO₂ aerogels were obtained by using sc-CO₂ drying from the TiO₂ wet gels. The conditions of sc-CO₂ drying were at 313, 323 K and 7.8–15.5 MPa. The electrodes with TiO₂ aerogel films were obtained by deposition of the aerogels on glass substrates. The electrodes with TiO₂ aerogel films and a commercial particle film of various thickness were obtained by repetitive coatings and calcinations. The amount of dye adsorbed on the TiO₂ films with sc-CO₂ drying was higher than that of commercial particle film. The amount of dye adsorbed on the TiO₂ films increased with increasing surface area of the TiO₂ film. DSSCs were assembled by using the TiO₂ aerogel film electrodes and their current–voltage performance was measured. The power performance of DSSC made by supercritical drying was higher than that of commercial particles. The DSSC with the film electrode made at 313 K and 15.5 MPa showed the best power performance (J_sc = 7.30 mA/cm², V_oc = 772 mV, η = 3.28%).     

Palygorskite and SnO2–TiO2 for the photodegradation of phenol

The photocatalytic removal of phenol was studied using palygorskite-SnO₂–TiO₂ composites (abbreviated as Paly-SnO₂–TiO₂) under ultraviolet radiation. The photocatalysts were prepared by attachment of SnO₂–TiO₂ oxides onto the surface of the palygorskite by in situ sol–gel technique. The products were characterized by XRD, TEM and BET measurements. SnO₂–TiO₂ nanoparticles, with an average diameter of about 10 nm, covered the surface of the palygorskite fibers without obvious aggregation. Compared with palygorskite-titania (Paly-TiO₂), palygorskite-tin dioxide (Paly-SnO₂), and Degussa P25, Paly-SnO₂–TiO₂ and SnO₂–TiO₂ exhibited much higher photocatalytic activity. The photodecomposition of phenol was as high as 99.8% within 1.5 h. The apparent rate constants (k_app) for Paly-SnO₂–TiO_2, TiO₂, and P25 were measured. Paly-SnO₂–TiO₂ showed the highest rate constant (0.03435 min^?1). The chemical oxygen demand (COD) of the phenol solution was reduced from 220.2 mg/L to 0.21 mg/L, indicating the almost complete decomposition of phenol. Reusability of the photocatalyst was proved.     

Photocatalytic reduction of CO2 on copper-doped Titania catalysts prepared by improved-impregnation method

Photocatalytic reduction of CO₂ by copper-doped titania catalysts has been investigated. The photocatalysts with various copper species (Cu⁰, Cu^I, Cu^II) were prepared by an improved-impregnation method, where copper nitrate is doped into TiO₂ Degussa-P25. It is likely that copper present on the catalyst surface and the grain size of copper–titania catalysts is uniform, with crystallite size approximately 23 nm. The dispersion capacity of CuO in the vacant sites of TiO₂ is about 4.16 Cu²⁺ nm⁻² (≈2.2 wt% of Cu), as indicated by XRD analysis. The activation energy (E_a) for Degussa-P25 and 3%CuO/TiO₂ is ca. +26 and +12 kJ/mol, respectively. These E_a values suggest that the desorption event is a rate limiting step, and the lower E_a of 3%CuO/TiO₂ may suggest a catalytic role of copper species that enhance the methanol production.     

Structural,thermal and electrical properties of Ti4+ substituted Bi2O3 solid systems

In the present study, the effect of TiO₂ doping on (1 ? x) Bi₂O₃ (x)TiO₂ (x = 0.05, 0.10, 0.15, 0.20) materials is investigated using X-ray diffraction (XRD), differential thermal analysis (DTA), ac conductivity, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). XRD results show the formation of single phase Bi₁₂TiO₂₀ at x ≥ 0.15 concentration of TiO₂. It is observed that, the lower concentration of TiO₂ leads to the formation of mixed phase. The x = 0.15 and x = 0.20 samples exhibit regular and uniform distribution of the grains as compared to x = 0.10 sample. The highest conductivity is observed for x = 0.15 specimen, e.g., 9 × 10^?7 S cm^?1.     

Synthesis and properties of TiO2 added NiNb2O6 microwave dielectric ceramics using a simple process

TiO₂ added NiNb₂O₆ ceramics produced using a reaction-sintering process were investigated. Pure columbite NiNb₂O₆ could be obtained without TiO₂ addition. With 30 and 40 mol% TiO₂ addition, a phase with the same structure of Ni_0.5Ti_0.5NbO₄ formed. Grain growth is easier in pellets with 30 and 40 mol% TiO₂ addition than in the NiNb₂O₆ pellets. Microwave dielectric properties: ?_r = 20.7, Q × f = 19,800 GHz (at 9 GHz) and τ_f = ?31.9 ppm/°C were obtained for NiNb₂O₆ pellets sintered at 1300 °C/2 h. ?_r around 45, Q × f = 5400–7700 GHz (at 6 GHz) and τ_f ～ 73 ppm/°C were obtained in pellets with 30 mol% TiO₂ addition. ?_r around 50, Q × f = 3800–5700 GHz (at 6 GHz) and τ_f ～ 99 ppm/°C were obtained in pellets with 40 mol% TiO₂ addition.     

Chemoselective synthesis of first representatives of bis(diorganothiophosphinyl)selenides, (R2P = S)2Se,from secondary phosphine sulfides and elemental selenium

First bis(diorganothiophosphinyl)selenides, (R₂P = S)₂Se, have been synthesized in 74–86% yield by the chemoselective interaction of secondary phosphine sulfides with elemental selenium (1:1 molar ratio, 100 °C, 3 h, 1,4-dioxane); the alternative bis(diorganoselenophosphinyl)sulfides, (R₂P = Se)₂S, are not formed under these conditions.     

Low temperature sintering of ZnTiO3/TiO2 based dielectric with controlled temperature coefficient

Structure, microstructure and dielectric properties of ZnTiO₃ and rutile TiO₂ mixtures (ZnTiO₃ + xTiO₂ with x = 0, 0.02, 0.05, 0.1, 0.15 and 0.2) sintered using ZnO–B₂O₃ glass phase (5 wt.% added) as sintering aid have been investigated. For all compounds, the sintering temperature achieves 900 °C. The X-ray diffraction patterns indicate for x = 0.1 that the material is composed by three phases identified as ZnTiO₃ hexagonal, TiO₂ rutile and ZnO. The presence of ZnO is explained by the introduction of Ti into Zn site to form the (Zn_1−xTi_x)TiO_3+x solid solution in resulting the departure of ZnO from the ZnTiO₃ structure. The ZnTiO₃ + 0.15TiO₂ composition sintered at 900 °C with glass addition exhibits attractive dielectrics properties (ɛ_r = 23, tan(δ) < 10⁻³ and a temperature coefficient of the dielectric constant near zero (τ_ɛ = 0 ppm/°C)) at 1 MHz. It is also shown that the introduction of TiO₂ allows to tune the temperature coefficient of the permittivity. All these properties lead this system compatible to manufacture silver based electrodes multilayer dielectrics devices.     

Synergic effect of cation doping and phase composition on the photocatalytic performance of TiO2 under visible light

The synergic effect of cation doping and phase composition for the further improvement of the photocatalytic activity of TiO₂ under visible light is reported for the first time. Fe^3 + and Sn^4 + co-doped TiO₂ with optimized phase composition were synthesized through a simple soft-chemical solution method. The visible-light-driven photocatalytic activity of Fe^3 + and Sn^4 + co-doped TiO₂ was 5 times of that of Evonik P25 TiO₂ using degradation of methylene blue as model reaction. The synthesized photocatalysts were characterized by powder X-ray diffraction, UV–Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, ¹¹⁹Sn Mössbauer spectroscopy, and X-ray absorption fine structure spectroscopy. It is indicated that Sn^4 + doping can facilitate the phase transition from anatase to rutile. The different ratios of anatase and rutile can be achieved by tuning the amount of Sn^4 + doped into the lattice. Furthermore, the doping of Sn^4 + into TiO₂ lattice can stabilize the phase composition when Fe^3 + is co-doped. In the Fe^3 + and Sn^4 + co-doped TiO₂, Sn^4 + is mainly used to tune and stabilize the phase composition of TiO₂ and Fe^3 + acts as a doping cation to narrow the band gap of TiO₂. Both band gap and phase composition of TiO₂ can be tuned effectively by the simultaneous introduction of Fe^3 + and Sn^4 +. The synergic effect of optimized phase composition (anatase/rutile = 25/75) and narrowed band gap should be the two main reasons for the promoted photocatalytic activity of TiO₂ under visible light.     

Control of refractive index by annealing to achieve high figure of merit for TiO2/Ag/TiO2 multilayer films

We modified the refractive index (n) of TiO₂ by annealing at various temperatures to obtain a high figure of merit (FOM) for TiO₂/Ag/TiO₂ (45 nm/17 nm/45 nm) multilayer films deposited on glass substrates. Unlike the as-deposited and 300 °C-annealed TiO₂ films, the 600 °C-annealed sample was crystallized in the anatase phase. The as-deposited TiO₂/Ag/as-deposited TiO₂ multilayer film exhibited a transmittance of 94.6% at 550 nm, whereas that of the as-deposited TiO₂/Ag/600 °C-annealed TiO₂ (lower) multilayer film was 96.6%. At 550 nm, n increased from 2.293 to 2.336 with increasing temperature. The carrier concentration, mobility, and sheet resistance varied with increasing annealing temperature. The samples exhibited smooth surfaces with a root-mean-square roughness of 0.37–1.09 nm. The 600 °C-annealed multilayer yielded the highest Haacke's FOM of 193.9×10⁻³ Ω⁻¹.     

Continuous hydrothermal synthesis of Ca1−xSrxTiO3 solid-solution nanoparticles using a T-type micromixer

In this work, a continuous hydrothermal synthesis method in supercritical water was applied to environmentally benign production of Ca_1−xSr_xTiO₃ (x = 0.0–1.0) solid-solution nanoparticles as key materials in conducting, electric, magnetic, and photocatalytic fields. A T-type micromixer (330 μm id) was introduced for rapid heating of stating solutions of Ca(NO₃)₂, Sr(NO₃)₂, and TiO₂ sol using turbulent flow mixing with preheated NaOH aqueous solution and also for exact control of reaction temperature. At 673 K and 30 MPa for 5.0 s mean residence time, Ca_1−xSr_xTiO₃ solid-solution nanoparticles having crystallite diameters of around 20 nm with monomodal diameter distributions were obtained without byproducts and production of CaTiO₃ and SrTiO₃ separately over the whole composition range. Effects of NaOH molality, Ca and Sr compositions in the starting solutions, and mean residence time on the reaction were examined. The results showed that TiO₂ sol dissolution and Ca_1−xSr_xTiO₃ precipitation were almost finished within 0.25 s mean residence time, and after that Ostwald ripening proceeded.