One-step synthesis of nanocrystalline N-doped TiO2 powders and their photocatalytic activity under visible light irradiation

Nanocrystalline N-doped TiO₂ powders were successfully prepared by hydrothermal reaction for 2 h at low temperature (120 °C) and at an applied pressure of 3 MPa. The grain size of the powders (calculated by use of Scherrer’s method) ranged from 8.2 to 10.2 nm. The BET specific surface area ranged from 151.0 to 220.0 m²/g. A significant shift of the light absorption edge toward the visible light zone was observed in the UV–visible spectra. XPS results showed that nitrogen atoms were incorporated into the TiO₂ lattice. The photocatalytic activity of the synthesized N-doped TiO₂ powders was evaluated by measurement of photodegradation of methylene blue (MB) in aqueous solution under visible light irradiation. The amount of MB degraded increased with increasing illumination intensity.     

Sol-gel preparation of Fe-doped mixed crystal TiO<Subscript>2</Subscript> powder and its photocatalytic activity for degradation of azo fuchsine under visible light irradiation

In this work, the Fe-doped mixed crystal TiO₂ photocatalyst which can utilize visible light was prepared by sol-gel and heat-treated methods. During heat-treatment, the phase transformation of Fe-doped TiO₂ powder occurs and the process is characterized by XRD and TG-DTA technologies. Otherwise, the sizes and shapes of Fe-doped and undoped TiO₂ powders were also compared using TEM images. The azo fuchsine in aqueous solutions, as a model compound, was treated under visible light irradiation using Fe-doped mixed crystal TiO₂ powders as photocatalyst. The results showed that, under visible light irradiation, the (0.25%) Fe-doped mixed crystal TiO₂ powder heat-treated at 600°C for 3.0 h behaved very high photocatalytic activities for degradation of azo fuchsine. The remarkable improvement of the photocatalytic activity of TiO₂ powder was elucidated through the cooperative effects of iron doping and phase transformation. The iron doping can restrain the recombination of photogenerated electron-hole pairs and the phase transformation can enhance the absorption of visible light. Furthermore, other influence factors such as azo fuchsine concentration, solution acidity, Fe3+ ion content and irradiation time were also studied. Thus, this method is applicable for the treatment of wastewater.     

Synthesis and visible light photocatalytic activity of Ag spot-coated TiO2–60 wt% SrO composite powders

Nano-sized TiO₂–60 wt% SrO composite powders were synthesized from titanium isopropoxide and Sr(OH)₂·8H₂O by use of a sol–gel method. Ag spot-coated TiO₂–60 wt% SrO composite powders containing 3, 5, or 7 wt% Ag were synthesized by hydrothermal-assisted attachment, by use of Ag hydrosol in a high-pressure bomb at 250 °C and 450 psi. Nano-sized Ag particles approximately 5–25 nm in diameter adhered to the TiO₂–60 wt% SrO₂ composite powders. The photocatalytic activity of Ag spot-coated TiO₂–SrO powders in the degradation of phenol showed that all were highly active when irradiated with UV light. TiO₂–60 wt% SrO composite powder spot-coated with 5 wt% Ag was more photocatalytically active under visible light than TiO₂–SrO composite powder.     

Excellent degradation performance of azo dye by metallic glass/titanium dioxide composite powders

The metallic glass/titanium dioxide powders (MG/TiO₂) with enhanced photocatalytic oxidation activity were synthesized, which exhibit a higher efficiency in decolorizing methylene blue solutions (MB). Compared with the pure TiO₂ and crystalline alloy/TiO₂ (CA/TiO₂) under the same circumstances, its degradation rate was 60 % and 30 % higher, respectively. Furthermore, compared with the CA/TiO₂, the MG/TiO₂ photocatalytic rate was three times faster when decolorizing MB. Considering the excellent intrinsic high-performance photocatalytic degradation under visible light irradiation, these novel powders were proven to have potential applications in water purification industry.     

Preparation of the visible light responsive TiO2 thin film photocatalysts by the RF magnetron sputtering deposition method

TiO₂ thin film photocatalysts which could induce photoreactions under visible light irradiation were successfully developed in a single process by applying an ion engineering technique, i.e., the radio frequency (RF) magnetron sputtering deposition method. The TiO₂ thin films prepared at temperatures greater than 773 K showed the efficient absorption of visible light; on the other hand, the TiO₂ thin films prepared at around 573 K were highly transparent. This clearly means that the optical properties of TiO₂ thin films, which absorb not only UV but also visible light, can be controlled by the preparation temperatures of the RF magnetron sputtering deposition method. These visible light responsive TiO₂ thin films were found to exhibit effective photocatalytic reactivity under visible light irradiation (λ > 450 nm) at 275 K for the reductive decomposition of NO into N₂ and N₂O. From various characterizations, the orderly aligned columnar TiO₂ crystals could be observed only for the visible light responsive TiO₂ thin films. This unique structural factor is expected to modify the electronic properties of a TiO₂ semiconductor, enabling the efficient absorption of visible light.     

Mesoporous interstitial and substitutional nitrogen-containing titanium dioxide photocatalysts prepared by acid-assisted sol–gel procedure

Two different types of nitrogen-containing TiO₂ were synthesized via an acid-modified sol–gel method. Yellow-colored interstitial and white substitutional nitrogen-containing TiO₂ powders were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller specific surface area and Barrett–Joyner–Halenda pore size distribution analyses, scanning electron microscopy, transmission electron microscopy and UV–vis absorption spectroscopy. The band gaps of interstitial and substitutional nitrogen-containing TiO₂ ceramics were estimated from UV–vis spectroscopy data to be 2.6 and 2.8 eV, respectively. Prepared substitutional nitrogen-containing TiO₂ featured steep light absorption edge with an approximately parallel characteristic to that in pure TiO₂. This fact is due to band-to-band visible light absorption ability of substitutional nitrogen-containing TiO₂. The photocatalytic properties of the produced nitrogen-containing TiO₂ samples were compared for the degradation of Direct Red 28 azo dye. Further studies were also devised to compare the catalytic efficiency of the nitrogen-containing TiO₂ powders with the pure TiO₂ synthesized via the similar sol–gel method. The produced nitrogen-containing TiO₂ samples revealed superior photocatalytic properties in comparison with pure TiO₂ due to their remarkable band gap narrowing, surface oxygen vacancies and much more surface defects. The results also revealed that the substitutional nitrogen-containing TiO₂ is the most effective photocatalyst under ultraviolet and visible light irradiation.     

Photocatalytic degradation of triazine dyes over N-doped TiO2 in solar radiation

Photocatalytic degradation of the reactive triazine dyes Reactive Yellow 84 (RY 84), Reactive Red 120 (RR 120), and Reactive Blue 160 (RB 160) on anatase phase N-doped TiO₂ in the presence of natural sunlight has been carried out in this work. The effect of experimental parameters like initial pH and concentration of dye solution and dosage of the catalyst on photocatalytic degradation have also been investigated. Adsorption of dyes on N-doped TiO₂ was studied prior to photocatalytic studies. The studies show that the adsorption of dyes on N-doped TiO₂ was high at pH 3 and follows the Langmuir adsorption isotherm. The Langmuir monolayer adsorption capacity of dyes on N-doped TiO₂ was 39.5, 86.0, and 96.3 mg g^?1 for RY 84, RR 120, and RB 160, respectively. The photocatalytic degradation of the dyes follows pseudo first-order kinetics and the rate constant values are higher for N-doped TiO₂ when compared with that of undoped TiO₂. Moreover, the degradation of RY 84 on N-doped TiO₂ in sunlight was faster than the commercial Aeroxide^® P25. However, the P25 has shown higher photocatalytic activity for the other two dyes, RR 120 and RB 160. The COD of 50 mg l^?1 Reactive Yellow-84, RR 120 and RB 160 was reduced by 65.1, 73.1, and 69.6 %, respectively, upon irradiation of sunlight for 3 h in the presence of N-doped TiO₂. The photocatalyst shows low activity for the degradation of RY 84 dye, when its concentration was above 50 mg l^?1, due to the strong absorption of photons in the wavelength range 200–400 nm by the dye solution. LC–MS analysis shows the presence of some triazine compounds and formimidamide derivatives in the dye solutions after 3 h solar light irradiation in the presence of N-doped TiO₂.     

Enhancement of visible-light photocatalytic activity of Cu-doped TiO<Subscript>2</Subscript> nanoparticles

Bare TiO₂ and Cu-doped TiO₂ nanoparticles with different nominal doping amounts of Cu ranging from of 0.5 to 5.0 mol% were synthesized using the modified sol–gel method. The samples were physically characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer–Emmett–Teller-specific surface area, UV–Vis diffuse reflectance spectroscopy, zeta potential, X-ray photoelectron spectroscopy, inductively coupled plasma, and photoluminescence techniques. The Cu-doped TiO₂ exhibited good photocatalytic activity in mineralization of oxalic acid and formic acid under visible light irradiation. Photomineralization of oxalic and formic acids under visible light irradiation revealed greatly enhanced photoactivity exhibited by the 2.0 mol% Cu-doped TiO₂ photocatalyst compared to bare TiO₂ . The enhanced photocatalytic performance arises from copper ion doping in the TiO₂ structure, leading to an extended photoresponsive range, enhanced photogenerated charge separation, and transportation efficiency.     

Plasma-Assisted Synthesis of TiO2 Nanorods by Gliding Arc Discharge Processing at Atmospheric Pressure for Photocatalytic Applications

The present study explores a new method of synthesis of TiO₂ nano-particles in an aqueous medium from TiCl₃ precursor by non-thermal plasma in humid air as feeding gas obtained at atmospheric pressure. The precursor solution, TiCl₃ is oxidized by strongly reactive species generated by gliding arc plasma (HO^· = 2.85 V/SHE) to produce titanium oxide powders. The synthesized powder was characterised by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, nitrogen physisorption, and UV–Vis spectroscopy. The results obtained showed that the material consists of rod-shaped nanoparticles of rutile and anatase phases. The presence of TiO₂ phases was confirmed by FTIR spectrum and textural analyses showed that the material is mesoporous with specific surface area of 158 m² g^?1. UV–Visible spectrum of the plasma-synthesized TiO₂ sample showed that it absorbs in the UV–A region leading to effective use as a photocatalyst under visible light.     

Sol–gel preparation and characterization of Ag and Mg co-doped nano TiO<Subscript>2</Subscript>: efficient photocatalytic degradation of C.I. Acid Red 27

In this study, we successfully prepared pure, mono-doped, and Ag, Mg co-doped TiO₂ nanoparticles using the sol–gel method, with titanium tetraisopropoxide as the Ti source. The prepared samples were characterized by X-ray powder diffraction (XRD), specific surface area and porosity (BET and BJH) measurement, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, photoluminescence, and energy dispersive X-ray spectroscopy techniques. The XRD data showed that the prepared nanoparticles had the same crystals structures as the pure TiO₂. Also, DRS results indicated that the band gap of co-doped photocatalyst was smaller than that of the monometallic and undoped TiO₂ and that there was a shift in the absorption band towards the visible light region. Furthermore, the photocatalytic activity of the prepared catalysts was evaluated by the degradation of C.I. Acid Red 27 in aqueous solution under visible light irradiation. The results showed that Ag (0.08 mol%), Mg (0.2 mol%) co-doped TiO₂ had the highest photoactivity among all samples under visible light. It was concluded that co-doping of the Ag and Mg can significantly improve the photocatalytic activity of the prepared photocatalysts, due to the efficient inhibition of the recombination of photogenerated electron–hole pairs. The optimum calcination temperature and time were 450 °C and 3 h, respectively.     

Azo dyes degradation using TiO2-Pt/graphene oxide and TiO2-Pt/reduced graphene oxide photocatalysts under UV and natural sunlight irradiation

The photocatalytic degradation of azo dyes with different structures (amaranth, sunset yellow and tartrazine) using TiO₂-Pt nanoparticles (TPt), TiO₂-Pt/graphene oxide (TPt-GO) and TiO₂-Pt/reduced graphene oxide (TPt-rGO) composites were investigated in the presence of UV and natural sunlight irradiation. The composites were prepared by a combined chemical-thermal method and characterized by Transmission Electron Microscopy (TEM), X-ray powder diffraction (XRD), Infrared (FTIR) and UV–Vis spectroscopy. The modification of TiO₂-Pt with graphene oxide shifted its optical absorption edge towards the visible region and increased its photocatalytic activity under UV and natural sunlight irradiation. The efficiency of catalysts on azo dyes degradation (in similar conditions) reached high values (above 99%) under sunlight conditions, proving the remarkable photocatalytic activities of obtained composites. TPt-GO nanocomposite exhibited higher photoactivity than TPt or TPt-rGO, demonstrating degradation efficiencies of 99.56% for amaranth, 99.15% for sunset yellow and 96.23% for tartrazine. The dye photodegradation process follows a pseudo-first-order kinetic with respect to the Langmuir-Hinshelwood reaction mechanism. A direct dependence between azo dyes degradation rate and chemical structure of dyes has been observed.     

Preparation of magnetically supported chromium and sulfur co-doped TiO2 and use for photocatalysis under visible light

Novel magnetic chromium and sulfur co-doped TiO₂ photocatalysts (M-Cr/S/TiO₂) have been prepared by a sol?Cgel process, using magnetic hollow fly ash microspheres as support material. The crystal phase of M-Cr/S/TiO₂ was characterized by X-ray diffraction, UV?Cvisible absorption spectroscopy, and transmission electron microscopy. The photocatalytic activity of the photocatalysts was examined by photodegradation of methyl orange in aqueous solution under visible light irradiation. The results showed that chromium and sulfur co-doped catalysts (Cr/S/TiO₂) containing 0.60?% (atomic ratio) chromium and 1.2?% (atomic ratio) sulfur calcined at 450?°C for 2?h had high catalytic efficiency under visible irradiation. It is worth mentioning that the floating M-Cr/S/TiO₂ catalyst had greater photocatalytic activity than Cr/S/TiO₂ powder. Therefore, M-Cr/S/TiO₂ is a promising, high-performing, visible-light-driven photocatalyst.     

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.     

Sol–gel synthesized vanadium doped TiO2 photocatalyst: physicochemical properties and visible light photocatalytic studies

Vanadium doped titanium dioxide (V–TiO₂) photocatalyst was synthesized by the sol–gel method using ammonium vanadate as vanadium source. The prepared samples were characterized by XRD, N₂ adsorption–desorption method, UV–Vis DRS, Fourier transform infrared (FTIR), scanning electron microscope–energy dispersive X-ray and photoluminescence (PL) analysis. The results show that V⁵⁺ ions were successfully incorporated into the crystal lattice of TiO₂ as a consequence, not only an obvious decrease in the band gap and a red shift of the absorption threshold into the visible light region was recorded for the V modified TiO₂, but, also a decrease in photogenerated electrons and holes recombination rate was observed as demonstrated by PL analysis. FTIR study indicated that in undoped TiO₂ sample the acetate group favored a bidentate bridging mode of binding with titanium atoms, whereas a bidentate chelating mode of linkage was observed in V–TiO₂ powders. The crystallite size of the samples calcined at 300 and 500 °C were decreased beyond the molar ratio of 200:1 (V:Ti), this may be due to dopant presence in the grain boundaries hindering the crystal growth. The photocatalytic activities for both pure and vanadium doped TiO₂ powders were tested in the discoloration of a reactive dyestuff, methylene blue, under visible light. The 100:1 (V:Ti) doped photocatalyst, calcined at 300 °C showed enhanced photocatalytic activity under visible light with a rate constant (k_obs) of 5.024 × 10^?3 min^?1 which is nearly five times higher than that of pure TiO₂, as result of low band gap value, high specific surface area and a decrease in recombination rate.     

Kinetics and mechanism of photocatalytic degradation of metobromuron by TiO2 in simulated sunlight

The kinetics of photocatalytic degradation of metobromuron in aqueous solution, with TiO₂ as photocatalyst under simulated sunlight irradiation, have been systematically investigated. The single-variable-at-a-time method and the central composite design based on response surface methodology were used to study the individual and synergistic effects of several classical conditions on the efficiency of photocatalysis. Three different conditions, TiO₂ concentration, pH, and initial concentration of metobromuron, were found to independently determine the efficiency of degradation. The optimum degradation conditions were: TiO₂ concentration 3.00 g/L, pH 7.88, and initial concentration of metobromuron 60.23 μM. In addition, a mechanism of degradation of metobromuron is tentatively proposed on the basis of the experimental results and theoretical calculation of frontier electron densities and point charges. The results suggest that substitution of the Br atom, addition of ·OH radicals, and the cleavage of urea side chain are the predominant degradation pathways during the initial stage of photocatalytic degradation.     

Research on photodegradation of formaldehyde by nanocrystalline N-TiO<Subscript>2</Subscript> powders under visible light irradiation

The photo-degradation of formaldehyde (HCHO) by nitrogen-doped nanocrystalline TiO₂ (N-TiO₂) powders under visible light irradiation has been systematically investigated. Experimental results show that the degradation ratio reached up to 42.6% after 2 h visible light irradiation when the amounts of N-TiO₂ powders were 0.5 g, the initial concentration of the HCHO was set at 0.98 mg/m³, the illumination intensity was fixed at 10,000 lux, the ambient temperature was set at 26 °C, and the relative humidity was maintained at 33 ± 5%. Further research shows that the degradation ratios were all larger than 40% in ten repeated cycles of photodegradation of HCHO by N-TiO₂ powders. The degradation ratio was as high as 82.9% after 2 h visible light irradiation when the amount of N-TiO₂ was 5 g. The degradation ratio was increased from 25.5 to 59.6% when the illumination intensity of the visible light was increased from 0 to 30,000 lux. However, the degradation ratio could not be further increased by further increasing the illumination intensity.     

TiO2/EDTA-rich carbon composites: Synthesis,characterization and visible-light-driven photocatalytic reduction of Cr(VI)

TiO₂/EDTA-rich carbon composites exhibits excellent photoreduction of Cr(VI) activity via ligand-to-metal charge transfer process.     

Amorphous titanium dioxide as an adsorbent for dye polluted water and its recyclability

Amorphous TiO₂, synthesized from TiCl₄ and diluted NH₃ solution, was characterized by X-ray diffraction spectrometry, UV–Vis diffused reflectance spectroscopy, Fourier-transformed infrared spectroscopy, and scanning electron microscopy. The powder exhibited high specific surface area at 508 m²/g as measured by the Brunauer-Emmett-Teller method. The pH at point of zero charge of the as-prepared amorphous TiO₂ was determined by the pH drift method to be 6.8. The product was studied for its sorption efficiency using two dyes—crystal violet (CV) and malachite green (MG). Studies on the effects of various sorption parameters (contact time, TiO₂ dosage, pH of solution, and initial concentration of dye) were carried out in order to find the optimum adsorption conditions for which the results were: contact time ~30 min, TiO₂ dosage ~0.05–0.1 g, pH 7–9, and initial concentration <1 × 10^?4 M. The adsorption data were analyzed and fitted better with the Langmuir model than the Freundlich model. The maximum adsorption capacities obtained from the Langmuir model were 0.4979 and 0.4075 mmol dye/g TiO₂ for CV and MG dye, respectively. In addition, the regeneration and the recyclability of the prepared amorphous TiO₂ were also studied. The used adsorbent should be regenerated 10–12 h before reuse in the next cycle for the best result.     

Light expanded clay aggregate (LECA) as a support for TiO<Subscript>2</Subscript>, Fe/TiO<Subscript>2</Subscript>, and Cu/TiO<Subscript>2</Subscript> nanocrystalline photocatalysts: a comparative study on the structure,morphology, and activity

In this work, TiO₂ and doped TiO₂ photocatalysts (Fe/TiO₂ and Cu/TiO₂) were synthesized by the sol–gel method. The main objective of this study was to investigate the influence of dopants on the structure, morphology, and activity of the catalysts in powder and immobilized states. XRF, XRD, and SEM methods were used to characterize the catalysts. The structure and phase distribution of the nanocrystalline powders were identified by XRD. Nanoparticles crystallite size and the degree of crystallinity were affected by doping. The anatase contents of catalysts were achieved as follows: TiO₂ (5.89 %) < Fe/TiO₂ (42.17 %) < Cu/TiO₂ (70.28 %). It was indicated that the activity of the catalysts strongly depends on the anatase content. Under the same circumstances, copper-modified TiO₂ exhibited a twofold higher photocatalytic activity compared with TiO₂. The nanostructured catalysts were immobilized on light expanded clay aggregate (LECA) granules in order to investigate the effect of a novel support on the activity of the catalysts. Morphological changes are recognizable in the SEM images. Activity tests indicated that the best catalytic performance was assigned to Cu/TiO₂/LECA. After 120 min of irradiation, 61 % degradation of phenol in synthetic wastewater was achieved. The high photocatalytic activity of Cu/TiO₂/LECA confirms that LECA is as an excellent support.     

Preparation of a visible light-driven Bi2O3–TiO2 composite photocatalyst by an ethylene glycol-assisted sol–gel method,and its photocatalytic properties

A visible light-driven Bi₂O₃–TiO₂ composite photocatalyst was prepared by an ethylene glycol-assisted sol–gel method in which ethylene glycol acted as a polycondensation agent to capture metal ions by reacting with bismuth and titanium sources via a complex polycondensation pathway. The photocatalyst was characterized by X-ray photoelectron spectroscopy, X-ray diffraction, acquisition of N₂ adsorption–desorption isotherms, transmission electron microscopy, and UV–visible diffuse reflectance spectroscopy. The results revealed that the Bi₂O₃–TiO₂ composite was of smaller particle size, greater specific surface area, and had stronger absorbance in the visible light region than pure TiO₂. The photocatalytic activity of the as-prepared catalyst was evaluated by degradation of rhodamine B under visible light irradiation (λ > 400 nm); the as-prepared Bi₂O₃–TiO₂ composite was substantially more active than pure TiO₂. This was ascribed to the high surface area and the heterojunction structure.