Hollow TiO2 containing multilayer nanofibers with enhanced photocatalytic activity

Hollow titania containing multilayer nanofibers was fabricated through the combination of electrospinning with layer-by-layer technique. Two different solvents, methylbenzene and THF were used to remove the template. The morphology of the obtained hollow multilayer nanofibers confirmed that THF is better than methylbenzene. The obtained hollow multilayer fiber has a diameter of about 700 nm and its shell thickness is about 140 nm. FTIR spectra show the fabrication of multilayer nanofibers. XPS measurement indicates that TiO₂ nanoparticles can be assembled successfully. The obtained multilayer hollow nanofibers have highest photocatalytic activity to degrade methylene blue solution comparing with the TiO₂ film due to their unique hollow structure.     

Facile preparation of Na-free anatase TiO2 film with highly photocatalytic activity on soda-lime glass

Na-free anatase TiO₂ film was prepared on soda-lime glass (SL-glass) from a TiF₄ aqueous solution upon addition of boric acid at 60 °C. It was found that the as-prepared TiO₂ film before calcination showed a higher photocatalytic activity than the calcined sample (500 °C). This could be attributed to the fact that the calcined TiO₂ film contained decent Na⁺ ions, which was diffused from the SL-glass substrate into the TiO₂ film during calcination, resulting in the decrease of photocatalytic activity.     

Synthesis of thermally stable mesoporous TiO2 and investigation of its photocatalytic activity

The effects of heat treatment, dopant type and thickness of sol layer, on the formation and stability of ordered TiO₂ mesostructure were investigated. Higher ageing temperature facilitates the separation of organic phase and inorganic phase, while thinner sol layer facilitates the formation of homogeneous system and improves the mesostructural order of TiO₂. Lanthanum dopant, which is more electropositive than Ti, can improve the thermal stability of mesostructure by enhancing the strength of Ti–O bond. On the contrary, Fe and Pd dopants, which are more electronegative than Ti, decrease the thermal stability of mesostructure. Furthermore, La doped mesoporous TiO₂ shows high activity in the photocatalytic degradation of Rhodamine B under the irradiation of visible light.     

Preparation of polyaniline-modified TiO2 nanoparticles and their photocatalytic activity under visible light illumination

Titanium dioxide nanoparticles were modified by polyaniline (PANI) using ‘in situ’ chemical oxidative polymerization method in hydrochloric acid solutions. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy spectrum (XPS) and UV–vis spectra were carried out to characterize the composites with different PANI contents. The photocatalytic degradation of phenol was chosen as a model reaction to evaluate the photocatalytic activities of the modified catalysts. Results show that TiO₂ nanoparticles are deposited by PANI to mitigate TiO₂ particles agglomeration. The modification does not alter the crystalline structure of the TiO₂ nanoparticles according to the X-ray diffraction patterns. UV–vis spectra reveal that PANI-modified TiO₂ composites show stronger absorption than neat TiO₂ under the whole range of visible light. The resulting PANI-modified TiO₂ composites exhibit significantly higher photocatalytic activity than that of neat TiO₂ on degradation of phenol aqueous solution under visible light irradiation (λ ≥ 400 nm). An optimum of the synergetic effect is found for an initial molar ratio of aniline to TiO₂ equal to 1/100.     

Synthesis and photocatalytic activity of TiO2-hectorite composites

TiO₂-hectorite composites were synthesized and characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Diffraction Spectrum (EDS) techniques. The course of composite formation, TiO₂ particles were intercalated into hectorite. The specific surface areas of the samples were determined by nitrogen adsorption. The composite with a Ti content 2.5% (m/m) had a higher specific surface area than other composites. Photocatalytic properties were tested in photooxidation of methylene blue (MB).     

Preparation, characterization and photocatalytic activity of Si-doped and rare earth-doped TiO2 from mesoporous precursors

Si-doped and rare earth-doped TiO₂ with large specific surface area were prepared by the hydrothermal method and sol–gel route, respectively, using C₁₈H₃₇NH₂ as template. The samples were characterized by XRD, FT-IR, low-temperature N₂ adsorption–desorption measurement, XPS and solid state UV–vis diffuse reflectance spectroscopy. The pore size for Si-doped TiO₂ exhibits both mesoporous and microporous distribution, and that for rare earth-doped TiO₂ exhibits a sharp and narrow distribution in microporous range. The photocatalytic activities were investigated with the degradation of phenol as probe reaction. Compared with pure TiO₂, the conversion of phenol and selectivity to CO₂ increases when adding rare earth elements, and the substitution of Si for Ti in an appropriate range also increases the conversion of phenol.     

Various TiO2 microcrystals: Controlled synthesis and enhanced photocatalytic activities

Titania microspheres with higher photocatalytic activity have been synthesized using TiCl₄ and FeCl₃ as the precursor in the presence of Span-80. The products were characterized with XRD, TEM and UV–vis DRS. XRD and TEM indicated that the microsphere was a mixture of rutile, brookite and anatase with a diameter of about 5–7 μm. The photocatalytic experiments revealed that the microspheres exhibited high photocatalytic activities under UV-light and solar irradiation. The degradation rate of methyl orange (MO) was 100% under UV-light irradiation for 3 h and 91% under solar irradiation for 6 h. In particular, the catalysts could be readily separated by sedimentation after the photocatalytic reaction.     

Enhanced photocatalytic activity of Au-buffered TiO2 thin films prepared by radio frequency magnetron sputtering

Au-buffered TiO₂ thin films have been prepared by radio frequency magnetron sputtering method. The structural and morphological properties of the thin films were characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic activity of the samples was evaluated by the photodecomposition of methylene blue. The Au-buffer thin layer placed between the TiO₂ thin films significantly enhanced photocatalytic activity by 50%. Annealing the Au-buffered TiO₂ thin film at 600 °C decreased the film roughness, but it increased the surface area and anatase crystalline size, enhancing the photocatalytic activity.     

Simple fabrication and photocatalytic activity of S-doped TiO2 under low power LED visible light irradiation

A series of S-doped TiO₂ with visible-light photocatalytic activity were prepared by a simple hydrolysis method using titanium tetrachloride (TiCl₄) and sodium sulfate (Na₂SO₄) as precursors. The photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV–vis diffuse reflectance spectrophotometer (UV–Vis DRS), and X-ray photoelectron spectroscopy (XPS). With the doping of S, photocatalysts with small crystal size, high content of anatase phase were obtained. The result showed that S-doped TiO₂ demonstrate considerably high photoactivity under low power visible LED light irradiation, while undoped TiO₂ and the Degussa P25 have nearly no activity at all. The possible mechanism of S-doped for the visible-light activity was discussed.     

HIPed TiO2 dense pellets with improved photocatalytic performance

The effects of heating method and temperature on physical, structural and photocatalytic behaviors of TiO₂ pellets prepared by conventional heating and hot isostatic pressing have been evaluated. The pellets of submicron TiO₂ powders were heated to 600, 650, 700, 750 and 1000 °C using both processing methods in order to compare anatase to rutile phase transformation and densification behaviors. Bulk densities and porosities were calculated using the Archimedes method. XRD analysis were performed to calculate anatase/rutile ratios. Microstructures were characterized using SEM. Photocatalytic experiments have been performed under full spectrum irradiation. Degraded methylene blue samples were periodically monitored through UV–vis spectrophotometer to determine degradation kinetics. Anatase to rutile transformation is slightly faster and densification is better for lower temperatures for conventional heating, however HIPing gives better densification above 750 °C as it also retards rutile transformation. Mixed phase structures and HIPed samples showed the best photocatalytic performance which makes this method advantageous.     

Fabrication and characterization of Ag–TiO2 multiphase nanocomposite thin films with enhanced photocatalytic activity

Ag–TiO₂ multiphase nanocomposite thin films were prepared on quartz substrates by the liquid phase deposition (LPD) method from a mixed aqueous solution of ammonium hexafluouotitanate, silver nitrate and boric acid under ambient temperature and atmosphere followed by calcination at 500 °C for 1 h. The grain growth of anatase was depressed upon Ag⁺ doping. However, silver ions not only promoted (or catalyzed) the formation of brookite phase but also reduced the phase transformation temperature of anatase to rutile. With increasing AgNO₃ concentration, the transmittance and band gap of the composite thin films decreased; however, the intensity of surface plasmon absorption (SPA) peaks increased and their peak position shifted to a longer wavelength range. When AgNO₃ concentration was higher than 0.03 M, the prepared samples consisted of anatase, brookite, rutile and metal silver nanocrystal particles, and their grain size ranges were 5–30 nm. The photocatalytic activity of the Ag–TiO₂ multiphase nanocrystal composite thin films prepared by this method exceeded that of pure TiO₂ thin films by a factor of more than 6.3 when AgNO₃ concentration was kept in the range of 0.03–0.05. This was attributed to the fact that there were many hetero-junctions, such as anatase/rutile, anatase/brookite, Ag/anatase, Ag/rutile and so on, existed in the Ag–TiO₂ multiphase nanocomposite films.     

Synthesis of 3D CQDs/urchin-like and yolk-shell TiO2 hierarchical structure with enhanced photocatalytic properties

A novel CQDs/TiO₂ hierarchical structure with enhanced photocatalytic properties was achieved by uniformly decorating urchin-like and yolk-shell TiO₂ microspheres (UYTMs) with carbon quantum dots (CQDs) through an environmentally friendly hydrothermal process. The CQDs were firstly synthesized by the electrochemical method, and the TEM, Raman and PL characterizations strongly indicated that the as-prepared CQDs exhibited good dispersion, high crystallinity and unique up-conversion properties. The UYTMs synthesized by a NaOH-assisted hydrothermal process showed stable 3D hierarchical structure and large surface area, which was beneficial for light absorption and contacting with contamination. The good combination of CQDs and UYTMs was further successfully achieved during the hydrothermal process, and demonstrated by a series of tests. The photocatalytic experiments suggested that the CQDs/UYTMs exhibited better photocatalytic activities than the pure UYTMs and P25 under both visible and UV light irradiation. The CQDs/UYTMs combining with 6?wt% of CQDs showed the best photocatalytic efficiency, while excessive CQDs tended to inhibit the photocatalytic activity. According to the results and discussions, a possible mechanism in improving the photocatalytic efficiency of the CQDs/UYTMs is significantly proposed. The up-conversion property of CQDs can broaden the absorption spectrum of CQDs/UYTMs to the visible light. Moreover, the CQDs, as the electron reservoirs, are efficient to separate the electrons and holes, leading to an improved photocatalytic activity of CQDs/UYTMs.     

Low temperature preparation and characterization of nanospherical anatase TiO2 and its photocatalytic activity on Congo red degradation under sunlight

Nanospherical titanium oxide with anatase structure was obtained at low temperature and normal pressure using a simple method of preparation. The dilute titanium (III) chloride solution was stirred at room temperature for several hours, and then ammonium hydroxide with hydrogen peroxide was added. A yellow gel TiO₂·xH₂O was obtained with nanodot shape and amorphous structure. Heated at 300 °C, it crystallized to pure anatase structure with nanospherical shape. The anatase particles prepared show good adsorption and photodegradation of Congo red solution under the sunlight. Materials were characterized by powder X-ray diffraction, thermal analysis, transmission electron microscope and UV spectroscopy.     

Structural and photocatalytic degradation characteristics of hydrothermally treated mesoporous TiO2

Mesoporous TiO₂ photocatalysts have been synthesized using polyethylene glycol (PEG) as a template direction agent in diluted acetic acid aqueous solution. This medium slows down the hydrolysis reaction of titanium sources due to the hydrolytic retardant and the strong chelating effects of acetic acid. A hydrothermal treatment process was introduced to better control the resultant mesoporous structures. The effects of PEG molecular weight and thermal treatment temperature on the resultant structure and photoactivity were investigated. Morphological, structural and phase compositional properties of the resultant photocatalysts were systematically characterized using transmission electron microscopy, X-ray diffraction and nitrogen adsorption/desorption analysis. The mesoporous structure with diameters between 13.3 and 17.0 nm and mean porous sizes that ranged from 9.6 to 13.3 nm were obtained when the molecular weight of PEG were varied from 200 to 20,000. The mesoporous diameters were changed significantly from 9.8 to 18.4 nm with mean porous sizes slightly increasing from 8.0 to 10.0 nm when the calcination temperature was varied from 350 to 550 °C. The activities of the resultant TiO₂ photocatalysts were evaluated using 2,4,6-tribrominated phenol as a testing compound that represents a class of toxic brominated flame retardants. The experimental results revealed that the photocatalytic activity depends on the phase and on the structural characteristics of the resultant photocatalysts.     

Gas-phase photocatalytic degradation of trichloroethylene on pretreated TiO2

This paper reports the effects of preillumination, prechlorination and prehydroxylation of TiO₂ glass fiber cloth (TiO₂-GFC) on the photocatalytic degradation (PCD) reaction of trichloroethylene (TCE) in gas–solid regime. The reaction was monitored in situ by FT-IR spectroscopy at room temperature (298 K). Product analysis by gas chromatography–mass spectrometry (GC–MS) revealed the formation of a new by-product, 1,1-dichloroethane (1,1-DCE) in significant amount along with other known by-products. The photocatalytic activities of TiO₂-GFC and the mineralization of TCE were dependent on preillumination, prehydroxylation and prechlorination while the product yield was significantly influenced by prehydroxylation and prechlorination of TiO₂-GFC. Prechlorination increased the yields of phosgene (COCl₂) and pentachloroethane (C₂HCl₅) while prehydroxylation decreased the yield of COCl₂ with corresponding increases in the yield of oxalyl chloride (COClCOCl) and the mineralization of TCE, suggesting a possible surface-mediated hydrolysis of phosgene to COClCOCl in the latter case. Reaction schemes have been proposed to account for the formation of 1,1-DCE and COClCOCl. The photocatalytic activity of TiO₂-GFC and the mineralization of TCE have been found to correlate with the concentration of HCl employed for the prechlorination of TiO₂-GFC.     

TiO2/BiOI/CQDs: Enhanced photocatalytic properties under visible-light irradiation

In this study, TiO₂/CQDs(TC), TiO₂/BiOI(TB), TiO₂/BiOI/CQDs(TBC) were prepared via a step-by-step method. Photocatalytic properties of the samples were carried out under visible-light irradiation using methyl orange (MO) as the target molecular. Among the samples, TBC showed the best photocatalytic performance, and the photocatalytic efficiency of TBC was more than 2 times higher than that of TiO₂, TC and TB samples, respectively. The reasons for the improved photocatalytic performance were discussed in this paper.     

A novel two-step method to synthesize lotus-leaf-structured TiO2 nanocrystals with good photocatalytic activity

Lotus-leaf-structured TiO₂ nanocrystals were prepared by a novel simple two-step method. TiO₂ nanocrystals obtained by two-step method exhibited better photocatalytic activity than the as-prepared TiO₂ nanocrystal obtained by one-step liquid phase deposition method. Even compared with commercial TiO₂ photocatalyst with the smaller average size (~ 7 nm), lotus-leaf-structured TiO₂ nanocrystals exhibited better photocatalytic activity. The possible reason for the good photocatalytic activity was also investigated.     

Mn2O3/TiO2 nanofibers with broad-spectrum antibiotics effect and photocatalytic activity for preliminary stage of water desalination

Composite nanofibers consisting of Mn₂O₃ and TiO₂ were prepared by the electrospinning process, and tested as Gram-class-independent antibacterial agent and photocatalyst for organic pollutants degradation. Initially, electrospinning of a sol–gel consisting of titanium isopropoxide, manganese acetate tetrahydrate and poly(vinyl pyrrolidone) was used to produce hybrid polymeric nanofibers. Calcination of the obtained nanofibers in air at 650 °C led to produce good morphology Mn₂O₃/TiO₂ nanofibers. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the as-spun nanofibers and the calcined product. X-ray powder diffractometry (XRD) analysis was also used to characterize the chemical composition and the crystallographic structure of the sintered nanofibers. The antibacterial activity of Mn₂O₃/TiO₂ nanofibers against Gram negative and Gram positive bacteria was investigated by calculating the minimum inhibitory concentration after treatment with the nanofibers. Investigations revealed that the lowest concentration of Mn₂O₃/TiO₂ nanofibers solution inhibiting the growth of Staphylococcus aureus ATCC 29231 and Escherichia coli ATCC 52922 strains is 0.4 and 0.8 μg/ml, respectively. Incorporation of Mn₂O₃ significantly improved the photodegradation of methylene blue (MB) dye under the visible light irradiation due to enhancing rutile phase formation in the TiO₂ nanofibers matrix.     

Facile in-situ Solvothermal Method to synthesize double shell ZnIn2S4 nanosheets/TiO2 hollow nanosphere with enhanced photocatalytic activities

The design and construction of efficient visible light responsive composite photocatalysts with intimate interfacial contacts in photocatalytic field have attracted huge interest. Herein, a double-shelled ZnIn₂S₄ nanosheets/TiO₂ hollow composite single nanosphere (ZIS/TiO₂) was first fabricated by a facile hydrothermal process, where 2D ZnIn₂S₄ nanosheets self-assembled on the external surface of TiO₂ hollow nanosphere to form the double-shelled hollow single sphere. The morphologies, structures, optical properties of as-prepared double-shelled ZIS/TiO₂ hollow nanospheres were characterized in detail. The photocatalytic activities of double-shelled ZIS/TiO₂ nanospheres for the photodegradations of Tetracycline hydrochloride, Levofloxacin and Rhodamine B under visible light irradiation have been investigated. Compared to pure TiO₂ and ZnIn₂S_4, the obtained ZIS/TiO₂ samples have significantly improved photocatalytic performances. The most optimal photocatalytic activity of ZIS/TiO₂-2 nanocomposite with 64 wt% ZnIn₂S₄ nanosheets coated is observed, and its degradation rate constant is 2.32 and 2.14 times as high as those of pure TiO₂ and ZnIn₂S₄. The superior photocatalytic performance of ZIS/TiO₂ nanocomposite can be ascribed to its unique double shell hollow structure and the synergistic effect between ZnIn₂S₄ and TiO₂. Our result provides some guidance for designing novel morphologies of composite photocatalyst with good photocatalytic performance.