Facile assembly of TiO2 nanospheres/SnO2 quantum dots composites with excellent photocatalyst activity for the degradation of methyl orange

In this report, SnO₂ quantum dots anchored on TiO₂ nanospheres (TiO₂/SnO₂ composites) have been synthesized by a simple one-step hydrothermal process, and then employed as photocatalyst in photodegradation system. The microstructure of TiO₂/SnO₂ composites reveals that the SnO₂ quantum dots are dispersed on the surface of TiO₂ nanospheres uniformly. The photocatalytic behavior of the as-prepared samples revealed that the composites exhibited highly efficient performance by degrading 100 mL of 10 mg/L methylene orange in 15 min completely under ultraviolet-visible light. Owning to the special structure of the composites, TiO₂/SnO₂ shows a more UV–vis light absorption than either pure TiO₂ nanospheres or pure SnO₂ quantum dots. This study offers a facile method to prepare TiO₂/SnO₂ composites, which will be a choice for greatly extending potential applications in water pollution treatment, degradation of pollutants and other related fields.     

Sol-gel synthesis of new TiO2/activated carbon photocatalyst and its application for degradation of tetracycline

A new efficient photocatalyst consisting of TiO₂-activated carbon composite (TiO₂/AC) was synthesized by sol-gel process and applied to decomposition of tetracycline (TC). Its properties and catalytic activity were evaluated in comparison with bare TiO₂ and P25, based on several characterization techniques and TC photodegradation kinetic studies. The results showed TiO₂/AC has better structural and electronic features for photocatalysis; S_BET of 129 m² g^–1, exclusively anatase phase, crystal size of 8.53 nm and band gap energy of 3.04 eV. The catalytic activity of the material was evaluated based on photodegradation kinetic studies of TC from aqueous solution (with initial concentration=50 mg L⁻¹ and catalyst dosage=1.0 g L⁻¹). Non-linear kinetic model of pseudo-first order were fitted to the resulting experimental data. The apparent first-order rate constant (k_app=42.9×10^–3 min^–1) and half-life time (t_1/2=16.1 min) determined for TiO₂/AC were better than those for P25 and bare TiO₂. TC degradation by-products were investigated by HPLC-MS, showing TC was completely degraded after 75 min, producing fragments with m/z smaller than 150.     

Photocatalytic degradation of dairy effluent using AgTiO2 nanostructures/polyurethane nanofiber membrane

Dairy effluent (DE) is environmentally toxic and needs special attention. Photocatalytic degradation of DE was studied using novel polyurethane (PU)-based membranes. Typically, silver–titanium dioxide nanofibers (AgTiO₂ NFs) and silver–titanium dioxide nanoparticles (AgTiO₂ NPs) were individually incorporated in PU electrospun nanofibers to overcome the mandatory sophisticated separation of the nanocatalysts, which can create a secondary pollution, after the treatment process. These nanomembranes were characterized in SEM, TEM, XRD and UV studies. The polymeric electrospun nanofibers were smooth and continuous, with an average diameter of about 550 nm, and held their nanofibrous morphology even after more than 2 h of photocatalytic degradation of DE, due to the good stability of PU in the aqueous solutions, which indicates good imprisoning of the functional photocatalysts. The PU–AgTiO₂ NPs and PU–AgTiO₂ NFs were effective materials for degradation of DE, even after two successive cycles. PU–AgTiO₂ NPs and PU–AgTiO₂ NFs showed a maximum degradation of 75% and 95%, respectively after 2 h. The significant enhancement of degradation in the PU–Ag–TiO₂ NPs and PU–Ag–TiO₂ NFs is attributed to the photoactivity of Ag–TiO₂ material under visible light irradiation.     

Optimization of flocculation conditions for the separation of TiO2 particles in coagulation-photocatalysis hybrid water treatment

TiO₂ mediated photocatalysis can decompose organic micropollutants (e.g., 1,4-dioxane) in water, but the removal of used TiO₂ particles is challenging. Although retrofitting enhances the particle separation efficiency, optimizing a coagulation/flocculation process should be most suitable for existing treatment plants. Therefore, the present study investigated the separation characteristics of TiO₂ particles added to drinking water treatment processes along with a polyaluminum coagulant. TiO₂ photocatalysts were able to achieve significant degradation of 1,4-dioxane (∼100% within 50 min) as well as dissolved organic matter (∼75% within 150 min) at a TiO₂ dose of 1.0 g/L under UV irradiation. Although the TiO₂ particle separation efficiency was sensitive to G values, maximal removal occurred at a G value of <34 s⁻¹ with a coagulant concentration of >8 mg/L as Al₂O₃. Sand filters had the capability to remove residual turbid materials and thus, the turbidity of the final product water dropped to as low as 0.1 NTU when the coagulation/flocculation process was preceded. The final effluent quality was comparable to that of a 0.45-μm membrane filter. The post separation of the TiO₂ photocatalysts dispersed for emergency water treatment to degrade 1,4-dixoane was successfully achieved with an optimal coagulant dose, proper flocculation, and sand filtration.     

Residence time distribution analysis and optimization of photocatalysis of phenazopyridine using immobilized TiO2 nanoparticles in a rectangular photoreactor

Optimization of photocatalytic degradation of phenazopyridine (PhP) under UV light irradiation using immobilized TiO₂ nanoparticles was studied. The effect of operational parameters was investigated using response surface methodology (RSM). Maximum removal efficiency was achieved at the optimum conditions: initial drug concentration of 10 mg/L, UV light intensity of 47 W/m², flow rate of 200 mL/min, and reaction time of 150 min. The residence time distribution (RTD) analysis was studied to find the effect of flow rate on the drug removal efficiency. The tracer (PhP) pulse injection response was studied with UV–vis measurements and was used to prepare RTD curves.     

Synthesis and catalytic properties of novel POM@TiO2 composite materials

Donor–π-bridge–acceptor (D–π–A) type polyoxometalates (POMs) were self-assembled for the first time on the surface of titanium dioxide (TiO₂) nanoparticles through the layer-by-layer (LBL) method. The obtained composite materials POM@TiO₂ were characterized by Transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FTIR), Raman spectrum and energy dispersive X-ray (EDX) spectroscopy. Catalytic properties of POM@TiO₂ were also investigated by treating organic pollutants (typically, removal of 40 mL 20 mg L^− 1 methylene blue (MB) by 10 mg POM@TiO₂ was up to 99.5% within 3 min under ambient conditions and the photodegradation efficiency was obviously higher than bare TiO₂ nanoparticles under irradiation).     

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.     

Synthesis and photocatalysis of TiO2 hollow spheres by a facile template-implantation route

Process variables such as reaction temperature (55 to 90 °C), calcination temperature (450 to 750 °C), and concentration of TiCl₄ precursor (26 to 105 mM) have been examined in order to tailor the surface area, crystallite size, and the anatase/rutile ratio of the polycrystalline TiO₂ microcapsules prepared by a template-implantation route in heptane solvent. The hollow capsules are all non-aggregating with nanoporous shell structure. Among the process variables examined, the Brunauer–Emmett–Teller (BET) surface area and the anatase/rutile ratio are found critically dependent on the reaction temperature, in which a reduced reaction temperature (from 90 to 55 °C) leads to a higher BET value (from 8.4 to 36.4 m^?2 g^?1), a predominant anatase phase (weight fraction of the anatase phase increases from 0.20 to 0.84), and an improved photodegradation of aqueous methylene blue (MB) dye under UV exposure (the degradation rate increases from 0.5×10^?2 to 5.5×10^?2 min^?1).     

Application of TiO2/perlite photocatalysis for degradation of ammonia in wastewater

The purpose of this study was removal of ammonia by a new photocatalytic process from synthetic wastewater under UV irradiation. TiO₂ was used as the photocatalyst and immobilized on perlite granules as a supporter. The prepared catalysts were characterized by SEM and FTIR analysis showed that TiO₂/perlite catalyst has mesoporous structures and uniform coating of TiO₂ on support. Also, the optimum efficiency of photocatalytical degradation of ammonia was obtained at pH 11 for UV intensity irradiation with 125 W lamp. About 68% degradation of ammonia in wastewater was achieved after 180 min of irradiation by using the optimized reaction conditions.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Visible light-driven mesoporous Au–TiO2/SiO2 photocatalysts for advanced oxidation process

Au–TiO₂/SiO₂ heterogeneous catalysts with different Au contents were successfully synthesized by a facile hydrothermal process and their photocatalytic activity towards reduction of Rose Bengal (RB), Methyl Blue (MB), Rhodamine B (RhB) and Congo Red (CR) was investigated in the presence of sodium borohydride (NaBH₄) for advanced oxidation process (AOP). The results reveal that 3 wt% Au loaded in TiO₂/SiO₂ can significantly degrade high RB concentration dye (>95%, 0.3 g/L, 12 pH) within 20 min of irradiation time. All catalysis reaction followed the pseudo-first order rate reaction with high correlation coefficient. The effect of loading of Au nanoparticles (1–5 wt%) along with variation in dye concentration (100–500 ppm), pH of solution (2–12), catalysts dosage (0.1–0.5 g/L), and reaction temperature (30–80 °C) were also studied. The present works shows the superior performance of Au–TiO₂/SiO₂ heterogeneous catalysts to be related to the high dispersion of Au nanoparticles in the TiO₂/SiO₂ and to the catalytic effect between gold and TiO₂.     

Fabrication of nitrogen-doped TiO2 monolith with well-defined macroporous and bicrystalline framework and its photocatalytic performance under visible light

In this study, hierarchically porous bicrystalline nitrogen-doped titania (N-doped TiO₂) monolithic material was fabricated by a simple two-step approach: (i) preparation of TiO₂ porous monolith by a sol–gel process of titanium alkoxide in a mild condition utilizing a chelating agent and mineral salt and (ii) annealing of TiO₂ porous monolith obtained under a modest flow of ammonia gas at 700 °C for 2 h. The phase composition, crystal structure, morphology, pore structure, and porous properties of the final product were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), mercury porosimetry, and nitrogen physisorption measurement, respectively. The resultant N-doped TiO₂ porous monolith possesses a bicrystalline (anatase and rutile) framework with a well-defined macroporosity. The results from X-ray photoelectron spectroscopy (XPS) confirm the formation of OTiN bonds in the N-doped TiO₂ porous monolith. The photocatalytic activity of N-doped TiO₂ porous monolith was evaluated by the photodegradation of Rhodamine B over the samples under visible light. Nearly 50% of Rhodamine B in aqueous solution was efficiently degraded by N-doped TiO₂ porous monolith with the mixed-phase of anatase and rutile under visible light within 120 min.     

Sol–gel reverse micelle preparation and characterization of N-doped TiO2: Efficient photocatalytic degradation of methylene blue in water under visible light

A series of N-substituted titanium (IV) 2-ethyl-1,3-hexanediolate Ti(C₃₂H₆₈O₈) precursor were synthesized by the sol–gel reverse micelle (SGRM) method. The ethylene diaminetetraacetic acid (Na₂EDTA) has been used as a source of nitrogen n species. The obtained solids were calcined at 500 ?C for 1 h to obtain photoactive phases. The effect of nitrogen content (N/Ti = 0.025; 0.03; 0.05 atomic ratios) is examined. The materials were characterized by XRD, BET, TG/DTA and UV–vis reflectance spectroscopy (DRS). Photocatalytic decolourisation of methylen blue (MB) in aqueous solution was carried out using nano, doped TiO₂. Experimental results revealed that N/Ti = 0.05 atomic ratio N-doped TiO₂ required shorter irradiation time for complete decolourisation of MB than pure nano TiO₂ and commercial (Degussa P-25) TiO₂.     

Electrophotocatalytic decolorization of an azo dye on TiO2 self-organized nanotubes in a laboratory scale reactor

It was investigated the feasibility of decolorization of an azo dye (DG 26) using a large scale nanotubular TiO₂ structured electrode in a laboratory photoelectrochemical reactor (0.8 L). Catalyst was grown by anodic oxidation directly on Ti surface and its microstructure and crystalline structure were characterized with SEM and XRD. TiO₂/Ti photoactivity under different anodic polarization values was evaluated via photoelectrochemical tests. The nanostructured TiO₂ was used in a reactor as photo-anode under UV monochromatic irradiation (254 nm) and it was subjected to bias (+ 1.5 V vs. SCE). A comparison with photolysis and photocatalysis processes was carried out under the same operating conditions to evaluate the synergistic action of photocatalysis and TiO₂/Ti electrochemical polarization.Electrophotocatalysis was proven to be more effective than photocatalysis in DG 26 decolorization. Catalyst polarization resulted in synergistic effect on process yields. The complete decolorization of a 40 mg/L solution of DG 26 was achieved in 24 h, without adding chemical reagents, and catalyst durability was demonstrated over 360 h tests. Therefore, the work done is challenging to prove that the process (irradiation + catalyst + polarization) is feasible and effectively up-grading to pilot and demonstrative scale applications after a fluid dynamics optimization of the photoreactor.     

Combustion synthesis of graphene oxide–TiO2 hybrid materials for photodegradation of methyl orange

Graphene oxide (GO)–TiO₂ hybrid materials with enhanced photocatalytic properties were synthesized by a one-step combustion method using urea and titanyl nitrate as the fuel and oxidizer, respectively. During the synthesis procedure, the precursors containing GO, fuel, and oxidizer were maintained at different combustion temperatures (300–450 °C) for 10 min to ignite the combustion reaction. The effects of combustion temperatures on the weight loss, chemical status and photocatalytic properties were studied by thermogravimetry and differential scanning calorimetry, X-ray photoelectron spectroscopy, Raman, and photoluminescence. GO in the GO–TiO₂ hybrids were not oxidized, but thermally reduced by decomposition of partial oxygen-containing groups. Meantime, the nitrogen doping of GO was achieved. Compared to the neat TiO₂ obtained at same condition, GO–TiO₂ hybrid obtained at 350 °C exhibited enhanced photodegradation performance, which is attributed to the effective photo-generated electron transferring from TiO₂ to partially reduced GO, which confirmed by the photoluminescence quenching of TiO₂.     

Preparation and characterization of CeO2–TiO2 support for Ru catalysts: Application in CWAO of p-hydroxybenzoic acid

The catalytic wet air oxidation of aqueous solutions of p-hydroxybenzoic acid has been carried out over CeO₂–TiO₂ supported ruthenium catalysts (Ru/Ce–Ti) at 140 °C and 50 bar of air. High activity of ruthenium supported catalysts was observed. It was found that the decrease of the molar ratio Ce/Ti from 3 to 1/3, improves the activity of Ru catalysts. The activity of the samples decreases in the following order: Ru/Ce–Ti (1/3) > Ru/CeO₂ ≈ Ru/TiO₂ > Ru/TiO₂DT51. Characterization of samples was performed by means of N₂ adsorption–desorption, XRD, UV–visible, TPR, SEM and TEM.     

Preparation and photocatalytic activity of silver and TiO2 nanoparticles/montmorillonite composites

Ag–TiO₂/montmorillonite (Ag–TiO₂/MMT) was synthesized as photocatalyst using TiCl₄ hydrolysis to introduce nanosized TiO₂ into the interlayer space of the montmorillonite (MMT). Stable pillared TiO₂/MMT was obtained by calcination at 500 °C, then silver was loaded by reduction of silver nitrate. The physico–chemical properties of the photocatalyst were determined by X-ray diffraction (XRD), infrared spectroscopy (IR), atomic absorption spectrophotometer (AAS), nitrogen gas adsorption (BET method) and UV–Visible spectra. The photooxidation activity for methylene blue (M.B.) degradation was as follows: Ag–TiO₂/MMT > TiO₂/MMT > TiO₂(P25). Among them Ag–TiO₂/MMT had the highest photooxidation activity because of its larger specific surface caused by pillaring and loading of silver for improving its light absorption.     

Enhanced photocatalytic degradation of rutile/anatase TiO2 heterojunction nanoflowers

Rutile/anatase TiO₂ heterojunction nanoflowers were prepared via a facile one-step hydrothermal approach using titanium tetrachloride and urea as the raw materials, cetyl trimethyl ammonium bromide (CTAB) as the template. The prepared TiO₂ nanoflowers were characterized by XRD, SEM, TEM and BET analyses. The photocatalytic performance of the as-prepared TiO₂ samples for methyl blue degradation under simulated solar light was investigated. TiO₂ heterojunction nanoflowers with mixed rutile/anatase phase (prepared with 3 mmol CTAB) give the highest photocatalytic activity. In addition, TiO₂ nanoflowers show excellent stability after 9 cycles under the same conditions. These results suggested that the mixed phase anatase/rutile TiO₂ heterojunction nanoflowers have great potential for the future photodegradation of real dye waste water.     

Preparation of graphene film decorated TiO2 nano-tube array photoelectrode and its enhanced visible light photocatalytic mechanism

Graphene film decorated TiO₂ nano-tube array (GF/TiO₂ NTA) photoelectrodes were prepared through anodization, followed by electrodeposition strategy. Morphologies and structures of the resulting GF/TiO₂ NTA samples were characterized by scanning electrons microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the optical and photoelectrochemical properties were investigated through UV–visible light diffuse reflection spectroscopy, photocurrent response and Mott–Schottky analysis. Furthermore, the photodecomposition performances were investigated through yield of hydroxyl radicals and photocatalytic (PC) degradation of methyl blue (MB) under visible light irradiation. It was found that GF/TiO₂ NTA photoelectrode exhibited intense light absorption both in UV light and visible region, higher transient photoinduced current of 0.107 mA cm⁻² and charge carrier concentration of 0.84 × 10¹⁹ cm⁻³, as well as effective PC performance of 65.9% for the degradation of MB. Furthermore, contribution of several reactive species to the PC efficiency of GF/TiO₂ NTA photoelectrode was distinguished. Moreover, the enhanced visible light PC mechanism was proposed and confirmed in detail.     

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.