Structure and photocatalytic properties of copper-doped rutile TiO2 prepared by a low-temperature process

Copper-doped titania with variable Cu/Ti ratios have been prepared via a simple aqueous-phase method at 85 °C. The obtained products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-vis absorption spectra analysis. The photocatalytic properties of the products were tested by photocatalytic degradation of aqueous brilliant red X-3B solution. The results showed that the sample with 2% copper doping has the best photocatalytic activity, which is 3 times that of undoped rutile titania. The effect of the doped copper on the structure and property of TiO₂ has also been discussed.     

Preparation and visible light photocatalytic activity of mesoporous N, S-codoped TiO2(B) nanobelts

The mesoporous N, S-codoped TiO₂(B) nanobelts are synthesized via hydrothermal synthesis and post-treatment, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption measurements (BET), X-ray photoelectron spectra (XPS), and UV-vis diffuse reflectance spectra (DRS). The results show that the prepared samples are mesoporous structured and exhibit stronger absorption in the visible light region with red shift in the absorption edge. The photocatalytic activity of N, S-codoped mesoporous TiO₂(B) nanobelts is evaluated by the photocatalytic photodegradation of potassium ethyl xanthate (KEX) under visible light irradiation. It is found that the photocatalytic activity of the prepared samples increases with increasing the molar ratio of thiourea to Ti (R). At R = 3, the photocatalytic activity of the N, S-codoped TiO₂(B) sample TBLTS-3 reaches a maximum value. With further increasing R, the photocatalytic activity of the sample decreases. The high photocatalytic activity of N, S-codoped TiO₂(B) nanobelts can be attributed to the balance between strong absorption in visible light region and low recombination rate of electron/hole pairs.     

Efficient visible-light-induced photocatalytic degradation of MO on the Cr-nanocrystalline titania-S

In order to improve visible light photocatalytic activities of the nanometer TiO₂, a novel and efficient Cr,S-codoped TiO₂ (Cr-TiO₂-S) photocatalyst was prepared by precipitation-doping method. The crystalline structure, morphology, particle size, and chemical structure of Cr-TiO₂-S were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) techniques, respectively. Results indicate that the doping of Cr and S, cause absorption edge shifts to the visible light region (λ > 420 nm) compare to the pure TiO₂, reduces average size of the TiO₂ crystallites, enhances desired lattice distortion of Ti, promotes separation of photo-induced electron and hole pair, and thus improves pollutant decomposition under visible light irradiation. The photocatalytic activities of Cr-TiO₂-S nanoparticles were evaluated using the photodegradation of methyl orange (MO) as probe reaction under the irradiation of UV and visible light and it was observed that the Cr-TiO₂-S photocatalyst shows higher visible photocatalytic activity than the pure TiO₂. The optimal Cr-TiO₂-S concentration to obtain the highest photocatalytic activity was 5 mol% for both of Cr and S.     

Highly active V-TiO2 for photocatalytic degradation of methyl orange

Two kinds of vanadium-doped TiO₂ powders photocatalysts were prepared by sol-gel method in even doping and uneven doping modes, and were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of TiO₂ photocatalysts doped by vanadium evenly with lower dopant level up to 0.002 mol.% is better than that of undoped TiO₂, while with higher dopant level the activity is worse. TiO₂ photocatalysts doped by vanadium unevenly with a p-n junction semiconductor structure, was shown to have a much higher photocatalytic destruction rate than that of TiO₂ photocatalysts doped by vanadium evenly and undoped TiO₂, which is ascribed mainly to the electrostatic-field-driven electron-hole separation in TiO₂ particles doped by vanadium unevenly.     

Effect of surface species on Cu-TiO2 photocatalytic activity

The Cu-TiO₂ nanoparticles with different Cu dopant content were prepared by sol-gel method. The structure of the as-prepared catalysts and the surface species of Cu-TiO₂ were determined using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and diffuse reflection spectroscopy (DRS). The relationship between the photocatalytic activity and the surface species of Cu-TiO₂ was revealed via the measurement of surface photovoltage spectroscopy (SPS) as well as the degradation of the rhodamine B (RhB). The experimental results suggest that the Cu-TiO₂ photocatalysts with appropriate content of Cu (about 0.06 mol%) possess abundant electronic trap, which effectively inhibits the recombination of photoinduced charge carriers, improving the photocatalytic activity of TiO₂. While at high Cu dopant region (>0.06 mol%), the excessive oxygen vacancies and Cu species can become the recombination centers of photoinduced electrons and holes. Meanwhile, at heavy Cu doping concentration, excessive P-type Cu₂O can cover the surface of TiO₂, which leads to decrease in the photocatalytic activity of photocatalyst. The photocatalytic experimental results are in good agreement with the conclusions of SPS measurements, indicating that there is a close relationship between the photocatalytic activity and the intensity of SPS spectra.     

Characterization and catalytic performance of pure and Li2O-doped CuO/CeO2 catalysts

Pure and Li₂O-doped CuO/CeO₂ catalysts calcined at 500 °C were prepared by impregnation method. The catalysts are characterized by DTA, TG-DTG, XRD, IR, TEM, nitrogen adsorption at −196 °C and the catalytic decomposition of hydrogen peroxide at 30 °C.The effects of molar ratio, heat treatment time and the doping on the structural, surface and catalytic properties of nanocrystalline Cu/Ce-mixed oxides system have been studied. It was found that the catalytic activity of ceria-supported copper oxide catalysts increased by increasing both the heat treatment time and dopant content. However, the pure Cu/Ce-mixed oxide solids containing 10 wt.% CuO exhibited the best performance. The characterization results indicated that the higher surface area, the formation of solid solution between copper and cerium oxides, and the high dispersion of copper species on the ceria were responsible for the high catalytic activity of the CuO/CeO₂ catalysts.     

Photocatalytic activity of multielement doped TiO2 in the degradation of congo red

TiO₂ although considered a promising photocatalyst for the degradation of aqueous pollutants, it suffers from poor absorption in the visible region and hence requires ultraviolet (UV) light for activation. To make TiO₂ a visible active photocatalyst, multielement (C, N, B, and F) doping has been done. The synthesised CNBF/TiO₂ catalysts were calcined at different temperatures and characterized by XRD, BET surface area, UV DRS, XPS, HRSEM-EDAX, and TEM techniques. These catalysts found to show less band gap values when compared to bare TiO₂. These catalysts were tested for their catalytic activity towards the degradation of a textile dye - congo red (CR) under different reaction conditions. It was found that the photocatalytic activity was dependent on both doping of multielement and the calcination temperature of CNBF/TiO₂. The co-doped catalysts which were calcined at 400 °C and 600 °C (100% intensity in anatase phase) were found to be the best catalysts (100% decolourisation of CR in 21/2 h and 2 h respectively). TOC analysis carried out for the samples at the reaction time of 5 h showed very high percentage (83%) degradation of CR over CNBF/TiO₂ catalysts calcined at 600 °C when compared to the other catalysts calcined at different temperatures. CNBF/TiO₂ (1000 °C) showed very less photocatalytic activity due to the formation of rutile phase.     

Ultrasound assisted synthesis of doped TiO2 nano-particles: Characterization and comparison of effectiveness for photocatalytic oxidation of dyestuff effluent

The present work deals with the synthesis of titanium dioxide nanoparticles doped with Fe and Ce using sonochemical approach and its comparison with the conventional doping method. The prepared samples have been characterized using X-ray diffraction (XRD), FTIR, transmission electron microscopy (TEM) and UV–visible spectra (UV–vis). The effectiveness of the synthesized catalyst for the photocatalytic degradation of crystal violet dye has also been investigated considering crystal violet degradation as the model reaction. It has been observed that the catalysts prepared by sonochemical method exhibit higher photocatalytic activity as compared to the catalysts prepared by the conventional methods. Also the Ce-doped TiO₂ exhibits maximum photocatalytic activity followed by Fe-doped TiO₂ and the least activity was observed for only TiO₂. The presence of Fe and Ce in the TiO₂ structure results in a significant absorption shift towards the visible region. Detailed investigations on the degradation indicated that an optimal dosage with 0.8 mol% doping of Ce and 1.2 mol% doping of Fe in TiO₂ results in higher extents of degradation. Kinetic studies also established that the photocatalytic degradation followed the pseudo first-order reaction kinetics. Overall it has been established that ultrasound assisted synthesis of doped photocatalyst significantly enhances the photocatalytic activity.     

Gallium- and iodine-co-doped titanium dioxide for photocatalytic degradation of 2-chlorophenol in aqueous solution: Role of gallium

Visible-light-driven TiO₂-based catalysts for the degradation of pollutants have become the focus of attention. In the present work, iodine-doped titania photocatalysts (I-TiO₂) were improved by doping with gallium (Ga,I-TiO₂) and the resulting physicochemical properties and photocatalytic activity were investigated. The structural properties of the catalysts were determined by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and transmission electron microscopy. We found that Ga probably enters the TiO₂ framework for doping levels <0.5 mol%. A further increase in Ga content probably leads to dispersal of excess Ga on the TiO₂ surface. The photocatalytic activity of Ga,I-TiO₂ catalysts was evaluated using 2-chlorophenol (2-CP) as a model compound under visible and UV-vis light irradiation. The results indicate that 0.5 mol% Ga loading and calcination at 400 °C represent optimal conditions in the calcining temperature range 400-600 °C and with doping levels from 0.1% to 1 mol%. The effective enhancement of 2-CP degradation might be attributed to the formation of oxygen vacancies by Ga doping, which could decrease the recombination of electron-hole pairs.     

Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.     

Photocatalytic Activities of Boron Doped Titanium Dioxide Nanoparticles and its Composite with Polyaniline

Abstract

Titanium dioxide (TiO₂) was doped with a nonmetalic element, boron (B), and the boron doped TiO₂ (B-TiO₂) was combined with polyaniline (Pani) through an in-situ polymerization technique. The photocatalytic activity of the prepared samples was monitored by the degradation of methylene blue under UV light irradiation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to reveal the effect of boron doping on the crystalline and chemical structure of the photocatalyst, respectively. The morphological and elemental compositional characteristics of the samples were evaluated using field emission scaning electron microscopy (FE-SEM) and energy dispersive x-ray analysis. The optical band gap energy of the prepared samples was obtained by UV-Visible (UV-Vis) spectroscopy. B-TiO₂ exhibited enhanced photocatalytic performance compared to the undoped photocatalyst. Furthermore, compared with TiO₂ and B-TiO₂, Pani/B-TiO₂ displayed superior photocatalytic activity. The composite achieved almost 26% methylene blue degradation within 150?minutes. Although the boron doping enhanced the crystallinity of TiO₂ slightly, it did not affect the morphology. FTIR confirmed the presence of tri-coordinated interstitial boron in the Ti–O–B bonds. The UV-Vis spectra displayed a red shift with the incorporation of the boron atoms. The incorporation of the boron atoms in the TiO₂ crystal structure are suggested to promote the separation of the photoinduced electron-hole pairs, a possible reason for the enhanced photocatalytic activity. B-TiO₂ and its composite with polyaniline could be considered as a promising photocatalyst to remove organic dyes from the wastewater.     

Enhanced photocatalytic activity and stability of nano-scaled TiO2 co-doped with N and Fe

Titanium dioxide (TiO₂) nanoparticles co-doped with N and Fe were prepared via modified sol-gel process. The products were characterized by transmission electron microscopy (TEM), N₂ adsorption, X-ray diffraction (XRD), Raman spectroscopy, UV-vis spectroscopy, photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). It is shown that the prepared TiO₂ particles were less than 10 nm with narrow particle size distribution. The addition of MCM-41 caused the formation of Ti-O-Si bond which fixed the TiO₂ on MCM-41 surface, thus restricted the agglomeration and growth of TiO₂ particles. The photocatalytic performance in the degradation of methylene blue showed that N, Fe co-doped TiO₂ exhibited much higher photocatalytic activity than doped sample with nitrogen or Fe³⁺ alone under both UV and visible light. N, Fe co-doping decreased the loss of doping N during the degradation reaction, thus increased the photocatalytic stability. It was also found that the nitridation time had significant influence on the photocatalytic activity of prepared TiO₂ catalysts.     

Structural, photochemical and photocatalytic properties of zirconium oxide doped TiO2 nanocrystallites

Composite photocatalysts composed of TiO₂ and ZrO₂ have been prepared via the sol-gel method. The as-prepared nanocomposites are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectrometry and fluorescence emission spectra. The results shows that TiO₂/ZrO₂ nanocomposites are composed of mainly anatase titania and tetragonal ZrO₂. Incorporating TiO₂ particles with ZrO₂ plays an important role in promoting the formation of nanoparticles with an anatase structure and leads to decreased fluorescence emission intensity. Most of the TiO₂/ZrO₂ nanocomposites exhibited comparable photocatalytic activity compared with commercial TiO₂ for the degradation aqueous methyl orange (MO) under ultraviolet irradiation, while the composite with Zr/Ti mass ratio of 15.2% shows the highest photocatalytic performances. Furthermore, the as-prepared nanocomposites can be reused with little photocatalytic activity loss. Without any further treatment besides rinsing, the photocatalytic activity of TiO₂/ZrO₂ (15.2%) composites is still higher than after five-cycle utilization.     

Synthesis of Titania-supported Copper Nanoparticles via Refined Alkoxide Sol-gel Process

Nanoparticles of titania and copper-loaded titania were synthesized by a refined sol-gel method using titanium butoxide. Unlike the conventional sol-gel procedure of adding water directly, the esterification of anhydrous butanol and glacial acetic acid provided the hydrolyzing water. In addition, acetic acid also served as a chelating ligand to stabilize the hydrolysis-condensation process and minimize the agglomeration of titania. Following the hydrolysis, Cu/TiO₂ was prepared by adding copper chloride to titania sol. The sol was dried, then calcined at 500^°C to remove organics and transformed to anatase titania which was verified by XRD. Cu/TiO₂ was further hydrogen-reduced at 300^°C. The recovery of Ti was exceeded by an average of 95% from titanium butoxide. TEM micrographs show that the Cu/TiO₂ particles are near uniform. The average crystallite sizes are 17–20 nm estimated from the peak broadening of XRD spectra. The bandgaps of TiO₂ and reduced Cu/TiO₂ range from 2.70 to 3.15 eV estimated from the diffusive reflective UV-Vis spectra. XPS analysis shows that Cu 2p_3/2 is 933.4 eV indicating primary Cu₂O form on the TiO₂ supports. The binding energy of Ti does not exhibit chemical shift suggesting negligible interaction of Cu cluster and TiO₂ support.     

Investigation of TiO2 photocatalyst performance for decolorization in the presence of hydrodynamic cavitation as hybrid AOP

In this article, an acoustic cavitation engineered novel approach for the synthesis of TiO₂, cerium and Fe doped TiO₂ nanophotocatalysts is reported. The prepared TiO₂, cerium and Fe doped TiO₂ nanophotocatalysts were characterized by XRD and TEM analysis to evaluate its structure and morphology. Photo catalytic performance of undoped TiO₂ catalyst was investigated for the decolorization of crystal violet dye in aqueous solution at pH of 6.5 in the presence of hydro dynamic cavitation. Effect of catalyst doping with Fe and Ce was also studied for the decolorization of crystal violet dye. The results shows that, 0.8% of Fe-doped TiO₂ exhibits maximum photocatalytic activity in the decolorization study of crystal violet dye due to the presence of Fe in the TiO₂ and it may acts as a fenton reagent. Kinetic studies have also been reported for the hybrid AOP (HAOP) that followed the pseudo first-order reaction kinetics.     

Preparation, characterization and photocatalytic activity of the neodymium-doped TiO2 nanotubes

A series of Nd-TiO₂ powders have been prepared by the sol-gel technique with neodymium nitrate and tetra-n-butyl titanium as raw materials, and then Nd-TiO₂ nanotubes were fabricated by the hydrothermal method with a 10 mol l⁻¹ NaOH solution. The as-prepared Nd-TiO₂ nanotubes were characterized by TEM, XRD, DRS, and XPS, and their photocatalytic activity was also tested in the case of the degradation of methyl orange in water. TEM photograph showed that Nd-TiO₂ nanotubes were about 10-20 nm in diameter, with the lengths range from 100 to 300 nm. TiO₂ nanotubes contained anatase and rutile crystallites. However, 0.3% Nd-TiO₂ nanotubes contained anatase crystallites, and only little rutile crystallites, so it is shown that neodymium doping hindered the phase transformation from anatase into rutile. Nd doping increased the visible-light absorption ability of Nd-TiO₂ nanotubes, and a red shift for Nd-TiO₂ nanotubes appeared when compared to TiO₂ nanotubes. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including metal-O and hydroxyl group, and more hydroxyl group was on the surface of 2% Nd-TiO₂ nanotubes than on the surface of TiO₂ nanotubes. Nd doping enhanced the photocatalytic activities of Nd-TiO₂ nanotubes, and 0.3% Nd-TiO₂ nanotubes exhibited the highest photocatalytic activity.     

Enhanced photocatalytic degradation of Safranin-O by heterogeneous nanoparticles for environmental applications

Nanostructure titanium dioxide (TiO₂) has been synthesized by hydrolysis of titanium tetrachloride in aqueous solution and Ag-TiO₂ nanoparticles were synthesized by photoreduction method. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy. The experimental results showed that the sizes of the synthesized TiO₂ and Ag-TiO₂ particles are in the range of 1.9-3.2 nm and 2-10 nm, respectively. Moreover, Ag-TiO₂ nanoparticles exhibit enhanced photocatalytic activity on photodegradation of Safranin-O (SO) dye as compared to pure TiO₂. The positive effect of silver on the photocatalytic activity of TiO₂ may be explained by its ability to trap electrons. This process reduces the recombination of light generated electron-hole pairs at TiO₂ surface and therefore enhances the photocatalytic activity of the synthesized TiO₂ nanoparticles. The effects of initial dye and nanoparticle concentrations on the photocatalytic activity have been studied and the results demonstrate that the dye photodegradation follows pseudo-first-order kinetics. The observed maximum degradation efficiency of SO is about 60% for TiO₂ and 96% for Ag-TiO₂.     

Effect of post heat treatment on microstructure and photocatalytic activities of TiO2 nanoribbons

Low-dimensional TiO₂ nanoribbons were synthesized by a simple one-step hydrothermal method. The TiO₂ nanoribbons were calcined over the temperature range 200-800 °C in order to enhance their photocatalytic properties by altering their crystal phase and increasing crystallization. Effects of hydrothermal temperature, calcinated temperature and calcination time on the formation of nanostructures have been observed and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The (BET) specific surface area of the samples which with different post treatments were determined by N₂ absorption-desorption experiment. In addition, photocatalytic activities of the nanoribbons were evaluated by photodegradation of organic dyes methyl orange under the radiation of UV light. The results reveal that the post-treatments have great effects on the microstructures and the photocatalytic activities of TiO₂ nanoribbons.     

A novel Ce, C-codoped TiO2 nanoparticles and its photocatalytic activity under visible light

A novel photocatalyst (Ce, C-codoped titania) was synthesized through a modified sol-gel method under mild condition. The as-prepared sample was investigated by XRD, SEM, DRS and XPS. It was found that the as-prepared photocatalyst was composed of spheroidal particles, which were smaller than undoped ones. The absorbance spectrum of Ce, C-codoped TiO₂ exhibited significant red-shift to visible region. It can be ascribed to appearance of a new electronic state in the middle of the TiO₂ band-gap. Furthermore, cerium doping could slow the radiative recombination process of photogenerated electrons and holes in TiO₂. Accordingly, for degradation of dye Reactive Brillint Red X-3B (C.I. reactive red 2) under visible light, the photocatalytic activity of Ce, C-codoped TiO₂ improved much compared to other samples (C-doped TiO₂, undoped TiO₂ and P25).     

Synthesis, characterization and degradation of Bisphenol A using Pr, N co-doped TiO2 with highly visible light activity

Praseodymium and nitrogen co-doped titania (Pr/N-TiO₂) photocatalysts, which could degrade Bisphenol A (BPA) under visible light irradiation, were prepared by the modified sol-gel process. Tetrabutyl titanate, urea and praseodymium nitrate were used as the sources of titanium, nitrogen and praseodymium, respectively. The resulting materials were investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV-vis absorbance spectroscopy, X-ray photoelectron spectroscopy (XPS), N₂ adsorption-desorption isotherm and Fourier transform infrared spectra (FTIR). It was found that Pr doping inhibited the growth of crystalline size and the transformation from anatase to rutile. The degradation of BPA under visible light illumination was taken as probe reaction to evaluate the photo-activity of the co-doped photocatalyst. In our experiments, the optimal dopant amount of Pr was 1.2 mol% and the calcination temperature was 500 °C for the best photocatalytic activity. Pr/N-TiO₂ samples exhibited enhanced visible-light photocatalytic activity compared to N-TiO₂, undoped TiO₂ and commercial P25. The nitrogen atoms were incorporated into the crystal of titania and could narrow the band gap energy. Pr doping could slow the radiative recombination of photogenerated electrons and holes in TiO₂. The improvement of photocatalytic activity was ascribed to the synergistic effects of nitrogen and Pr co-doping.