Application of solar light for degradation of ammonia in petrochemical wastewater by a floating TiO2/LECA photocatalyst

In this study, photocatalytic degradation of ammonia in petrochemical wastewater was investigated by solar light/TiO₂ photocatalysis. The TiO₂ nanoparticles were used as photocatalysts which were immobilized on light expanded clay aggregate (LECA) granules as a new porous and light weight support. Maximum concentration of ammonia (975 mg/L) in petrochemical wastewater was selected, and to optimize the photocatalytic reaction, the effect of pH and catalyst dosage was investigated in two aerated and agitated reactor systems. Also, the morphology and chemical structure properties of the prepared catalysts were characterized by SEM and XRF analyses. The experimental results were shown that the performance of two types of aeration reactor systems was almost the same. Also, the ammonia removal efficiency was increased by increasing the pH value, and after solar light irradiation in three days, the solar reactor system lead degradation of ammonia in pH = 11–96.5%. The floating of photocatalyst can be reused at least three consecutive times with 14% decreases on the ammonia removal efficiency. The results suggest that the photocatalytic purification followed by solar photocatalytic reactor would be a promising method for the purification of chemical wastewater.     

Self-cleaning ceramic tiles coated with Nb2O5-doped-TiO2 nanoparticles

In this work, 5 mol% Nb₂O₅-doped TiO₂ synthesized sol was sprayed on glazed ceramic tiles. The crystallization of TiO₂ nanoparticles occurs on the surface of the tiles after annealing at 600–900 °C, this innovative approach leads to a drastic decrease in the titania grain size as detected by SEM and XRD. The superhydrophilic and self-cleaning performance was evaluated by measuring the water contact angle under UV irradiation and by degradation of methylene blue according to ISO 10678 and JIS R1703-2. The results showed a high performance of doped samples at all temperatures tested, with a marked dependence on the anatase-to-rutile ratio and crystallite size. At 800 °C, the doped samples achieved water contact angle near to zero in just 15 min of UV irradiation, which confirms the high performance of the self-cleaning ceramic tiles.     

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.     

Solar photocatalytic decolorization of dyes in solution with TiO2 film

Application of TiO₂ film to solar photocatalysis of organic dyes, including Methylene Blue (MB) (λ_max, 660 nm), RR195 (λ_max, 540 nm) and RY145 (λ_max, 420 nm), was investigated. It was found that after 6-h solar irradiation, the extent of color degradation of dyes using solar photocatalytic system without TiO₂ film was quite limited. The color removal percentage for MB, RR195, and RY145 was found to be 23.3, −9.3, and −20.7%, respectively, resulting from competitions between the photosensitizing reaction and formation of colored intermediates during solar irradiation. However, as TiO₂ film was applied, the color degradation capability of solar photocatalytic system was significantly improved, in spite of the fact that only approximately 7% of solar irradiation belongs to the UV region. The color removal percentage for MB, RR195, and RY145 was up to 93.6%, 85.3%, and 71.1%, respectively, after 6-h irradiation. We believed that in such a solar photocatalytic system immobilized with TiO₂ film, both the maximum absorbance wavelength of the dye and the adsorbability of the dye on TiO₂ film played significant roles on the rate and efficiency of color removal of the dye solutions. Moreover, the possible reaction mechanism was proposed. The solar photocatalytic process with immobilized TiO₂ film was found to follow the pseudo-first order reaction kinetics. Color removal rate of MB was almost twice of that of RY145. Accordingly, the photocatalytic degradation process using solar light as an irradiation source, and immobilized TiO₂ as a photocatalyst, showed potential application for the decolorization of wastewater.     

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.     

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.     

Photocatalytic and adsorptive treatment of 2,4-dinitrophenol using a TiO2 film covering activated carbon surface

Anatase titanium dioxide (TiO₂) in particle sizes of roughly 0.5–20 μm was prepared from amorphous TiO₂ in an aqueous H₂O₂ solution by heating at 90 °C for 9 h and directly deposited on a PET film. On the other hand, granular activated carbon (AC) particles in sizes of 1–2 mm in diameter were adhesively deposited on a PET film, and their surfaces were also coated with TiO₂. The resulting three preparations (TiO₂-, AC-, and TiO₂/AC-PET films) were set up in an annular-flow reactor to treat aqueous solutions of 2,4-dinitrophenol (DNP) in a batch-recirculation mode. The rate of DNP adsorption onto the TiO₂/AC-PET film without UV irradiation was almost the same as that onto the AC-PET film, indicating that the attraction of DNP to AC was not lowered in the presence of TiO₂ film. Observation of SEM photographs suggests that this result is attributed to the porous structure of the thin TiO₂ film covering AC particles. The rate of DNP removal by the TiO₂-AC PET film under UV irradiation was 2.9 times higher than that by the TiO₂-PET film under UV irradiation, and was 1.1 times higher than the rate of DNP adsorption onto the AC-PET film. The rate of DNP removal by the AC-PET film decreased by 40% after six runs, while that by the TiO₂/AC-PET film decreased by 22%. Durable experiments using the TiO₂/AC-PET and AC-PET films clarified that the lifetime of the TiO₂/AC-PET film is at least two times longer than that of the AC-PET film. This result suggests that DNP molecules are photocatalytically decomposed when passing through the porous TiO₂-PET film, which lessens a burden of DNP adsorption on AC. Moreover, the DNP treatments in the batch-recirculation flow system suggested that the TiO₂/AC-PET film saturated with DNP can be successfully regenerated at 60 °C.     

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.     

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.     

The photo-catalytic activities of neodymium and fluorine doped TiO2 nanoparticles

A series of photo-catalysts were synthesized by neodymium and fluorine doped TiO₂, and their characteristics evaluated by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Neodymium and fluorine doped TiO₂ has obvious absorption in the visible light and the absorption edge shifts toward red wavelength. In addition, compared with pure TiO₂, the doped catalyst has intense absorption at 528, 587, 750, 808, and 881 nm. The catalytic efficiency was tested by monitoring the photo-catalytic degradation of methylene blue (MB) in visible light and ultraviolet light. The results showed that the optimum doping content was Nd:F:TiO₂ = 0.5:5:100 (molar ratio) heat treated at 500 °C, and the reaction rates of MB degradation were estimated to be about 1.76 times and 1.45 times higher than undoped TiO₂ in ultraviolet light and visible light.     

Photocatalytic degradation of methyl tert-butyl ether (MTBE) by Fe-TiO2 nanoparticles

Nowadays, since the underground waters are known as the main source for supplying the drinking water, their pollution to the organic contaminants such as methyl tert-butyl ether (MTBE) is a very significant issue. Therefore, in this study, photocatalytic degradation of MTBE was investigated in the aqueous soloution of Fe-TiO₂ nanoparticale under UV irradiation (wavelenght 254 nm) in a batch reactor. The Fe-TiO₂ mixed oxides were prepared by sol–gel impregnation method. The samples were characterized by X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM) and BET specfic surface area. Then, the effect of various operational parameters namely pH, catalyst loading, molar ratio of [H₂O₂]₀/[MTBE]₀ and UV light intensity on degradation of aqueous MTBE were evaluated in a batch reactor. The optimal condition to achieve the best degradation for the initial concentration of 75 ppm MTBE was found at pH 7, catalyst concentration 2 g/L, molar ratio of [H₂O₂]₀/[MTBE]₀ 4, and UV irradiation 24 W. Total degradation of MTBE with initial concentration of 75 ppm was reached in optimal condition after 70 min. In addition, investigations were also carried out to determine the appropriate kinetics of MTBE degradation using UV/Fe-TiO₂/H₂O₂ process in optimal condition.     

Effect of TiO2 nanoparticles on the antibacterial and physical properties of polyethylene-based film

TiO₂ nanoparticles and their application in packaging systems have attracted a lot of attention because of its antimicrobial activity. In this work, effect of TiO₂ nanoparticles on the antibacterial and physical properties of polyethylene (PE)-based film was investigated. Results indicated that the antibacterial activity of TiO₂-incorporated PE films should be due to the killing effect property of TiO₂ nanoparticles against microorganisms. The TiO₂-incorporated PE film exhibited more effective antibacterial activity for Staphylococcus aureus. The antibacterial activity to inactivate Escherichia coli or S. aureus was improved by UV irradiation. The inhibition ratio of TiO₂-incorporated PE films sample irradiated for 60 min by UV light was improved significantly, which were 89.3% for E. coli and 95.2% for S. aureus, respectively, compared to that of TiO₂-PE film without UV irradiation. The analysis of physical properties revealed that TiO₂ nanoparticles increased the tensile strength and elongation at break of PE-based film. The climate resistance of nano-TiO₂ films is greatly enhanced, compared to that of the blank PE film. Water vapor transmission increased from 18.1 to 24.6 g/m²·24 h with the incorporation of TiO₂ nanoparticles. Results revealed that PE based film incorporating with TiO₂ nanoparticles have a good potential to be used as active food packaging system.     

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.     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Synergy effect in the photocatalytic degradation of methylene blue on a suspended mixture of TiO2 and N-containing carbons

N-containing carbon materials were obtained from waste plum stones submitted to pyrolysis under Ar flow at 700 °C or to activation under steam at 800 °C and enriched with nitrogen by heating in a NH₃/air mixture at 270 °C or in NO at 300 °C. In situ mixtures of TiO₂ and carbons were prepared by the slurry method and methylene blue photodegradation was chosen as a model reaction to verify the influence of N-containing carbons on the photocatalytic activity of TiO₂ under artificial visible light irradiation. From the kinetics of methylene blue degradation an important synergy effect between both solids was detected with a remarkable increase up to a factor of 5.3 higher in the photocatalytic activity on TiO₂–C than that on TiO₂ alone. A mechanism for the photoassisting role of N-containing carbons upon the photoactivity of TiO₂ under visible light is discussed.     

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.     

Photocatalytic reduction of CO2 to energy products using Cu–TiO2/ZSM-5 and Co–TiO2/ZSM-5 under low energy irradiation

Copper or cobalt incorporated TiO₂ supported ZSM-5 catalysts were prepared by a sol–gel method, and then were characterized by XRD, BET, XPS and UV–vis diffuse reflectance spectroscopy. Ti^3 + was the main titanium specie in TiO₂/ZSM-5 and Cu–TiO₂/ZSM-5, which will be oxide to Ti^4 + after Co was doped. With the deposition of Cu or Co, the efficiency of the CO₂ conversion to CH₃OH was increased under low energy irradiation. The peak production rate of CH₃OH reached 50.05 and 35.12 μmol g^− 1 h^− 1, respectively. High photo energy efficiency (PEE) and quantum yield (φ) were also reached. The mechanism was discussed in our study.     

Preparation of novel nanometer TiO2 catalyst doped with upconversion luminescence agent and investigation on degradation of acid red B dye using visible light

An unreported nanometer TiO₂ photocatalyst doped with upconversion luminescence agent (40CdF₂ · 60BaF₂ · 0.8Er₂O₃) utilizing visible light was prepared. Its photocatalytic activity was checked through the photocatalytic degradation of acid red B as a model compound under visible light irradiation. Results show that the upconversion luminescence agent prepared as dopant can effectively turn visible lights to ultraviolet lights, which can be absorbed by nanometer TiO₂ particles to produce the electron-cavity pairs. Therefore, the photocatalytic ability of this novel TiO₂ photocatalyst has greatly been enhanced compared with undoped and common TiO₂ photocatalyst.     

Thermodynamic parameters of activation for photodegradation of phenolics

The photocatalytic degradation of three phenolics namely phenol, 4-chlorophenol and 4-nitrophenol were carried out in aerated aqueous suspension of TiO₂ irradiated by ultraviolet light. The influence of temperature at optimized pH and TiO₂ concentration was studied. The degradation kinetics were somewhat accelerated by increase in temperature in the range 25–45 °C and apparent activation energy was calculated to be 9.68–21.44 kJ mol^?1. Thermodynamic parameters of activation were also assessed for the degradation process. Formation of acidic species results in decrease in pH of solution. The appearance and the evolution of main intermediate species like hydroquinone, benzoquinone and catechol during the degradation process were computed by UV–vis spectral analysis.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.