Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Low-temperature hydrothermal synthesis of S-doped TiO2 with visible light photocatalytic activity

A one-step low-temperature hydrothermal route was developed for the synthesis of S-doped TiO₂ photocatalysts from TiS₂ and HCl. Crystalline TiO₂ was formed and sulfur could be efficiently doped into the anatase lattice under hydrothermal conditions. When the initial TiS₂ concentration is increased, the content of S-dopant and optical absorption in the visible region also increase. The photocatalytic activity of the S-doped TiO₂ was evaluated through the degradation of 4-chlorophenol under visible light irradiation. Our results show that the S-doped TiO₂ prepared by this hydrothermal approach possesses much higher photocatalytic activity than that obtained by the traditional high-temperature thermal annealing method.     

Enhancement of photocatalytic H<Subscript>2</Subscript> evolution over TiO<Subscript>2</Subscript> nano-sheet films by surface loading NiS nanoparticles

NiS/TiO₂ nano-sheet films (NiS/TiO₂ NSFs) photocatalysts were prepared by loading NiS nanoparticles as noble metal-free cocatalysts on the surface of TiO₂ films through a solvothermal method. The prepared samples were characterized by XRD, SEM, EDS, UV–Vis absorption spectra and XPS analysis. The photocatalytic H₂ evolution and photoluminescence spectroscopy (PL) experiments indicated that the NiS cocatalysts could efficiently promote the separation of photogenerated charge carriers in TiO₂ and consequently enhance the H₂ evolution activity. The hydrogen yield obtained from the optimal sample reached 4.31 μmol cm^–2 at 3.0 h and the corresponding energy efficiency was about 0.26%, which was 21 times higher than that of pure TiO₂ NSF. A possible photocatalytic mechanism of NiS cocatalyst on the improvement of the photocatalytic performance of TiO₂ NSF was also proposed.     

Nitrogen-doped TiO<Subscript>2</Subscript> nanopowders prepared by chemical vapor synthesis: band structure and photocatalytic activity under visible light

During chemical vapor synthesis of TiO₂ nanopowders, nitrogen atoms were doped into the crystal lattice of TiO₂. The nitrogen atoms were predominantly incorporated substitutionally in the crystal lattice of TiO₂ nanopowders up to the doping level of 1.25 mol% nitrogen, whereas they were in both interstitial and substitutional sites over about 1.43 mol% nitrogen. From the photocatalytic activity of nitrogen-doped TiO₂ estimated by decomposition of methylene blue under visible light, it was found that the substitutional nitrogen anions appearing at the low level doping was beneficial to its photocatalytic activity, whereas the interstitial ones appearing at the high level doping over 1.25 mol% nitrogen were not. The improved photocatalytic activity due to the substitutionally doped nitrogen was attributed to band gap narrowing which was confirmed by the studies of XPS, near edge X-ray absorption fine structure, and UV–Vis absorption.     

Synthesis and Characterization of Spindle-Like TiO<Subscript>2</Subscript> Nanostructures and Photocatalytic Activity on Methyl Orange and Methyl Blue Dyes Under Sunlight Radiation

Spindle-like TiO₂ nanostructures was prepared by a simple one pot solvothermal method followed by calcination at 400 °C for 3 h. The sample was characterized using various techniques such as X-ray diffractometer, transmission electron microscopy, Fourier transform infrared spectroscopy and UV–Vis absorption spectroscopy. The crystal structure of TiO₂ nanostructure was measured by X-ray diffractometer. According to the XRD result, the peaks in the sample can be indexed to anatase phase of TiO₂. The morphological characterization of TiO₂ sample was examined by transmission electron microscopy. The synthesized sample consisted of spindle-like shape with size in the range of 50–70 nm. The band gap value of Spindle-like TiO₂ nanostructures is 2.92 eV, which is lower than that of bulk TiO₂ of 3.2 eV. The FTIR bands observed at 493, 443 and 428 cm^?1 confirms the presence of TiO₂. The Spindle-like TiO₂ nanostructures showed photodegradation ability for methyl orange and methyl blue dye. The reuse evaluation of the Spindle-like TiO₂ nanostructures showed that their photocatalytic activity had good durability.     

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

B-doped TiO₂ nanotubes (B/TiO₂ NTs) were prepared by the combination of sol–gel process with hydrothermal treatment. The prepared catalysts were characterized by XRD, TEM and XPS. The photocatalytic activity of B/TiO₂ NTs was evaluated through the photodegradation of aqueous methyl orange. The results demonstrated that the 1.5% B/TiO₂ NTs calcined at 300 °C possessed the best photocatalytic activity. Compared with pure TiO₂ nanotubes, the doping with B significantly enhanced the photocatalytic efficiency.     

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.     

Hydrothermal synthesis of (Fe,N) co-doped TiO<Subscript>2</Subscript> powders and their photocatalytic properties under visible light irradiation

(Fe, N) co-doped titanium dioxide powders have been prepared by a quick, low-temperature hydrothermal method using TiOSO₄, CO(NH₂)₂, Fe(NO₃)₃, and CN₃H₅ · HCl as starting materials. The synthesized powders were characterized by XRD, TEM, BET, XPS, and UV–Vis spectroscopy. Experimental results show that the as-synthesized TiO₂ powders are present as the anatase phase and that the N and Fe ions have been doped into the TiO₂ lattice. The specific surface area of the powders is 167.8 m²/g by the BET method and the mean grain size is about 11 nm, calculated by Scherrer’s formula. UV–Vis absorption spectra show that the edge of the photon absorption has been red-shifted up to 605 nm. The doped titanium dioxide powders had excellent photocatalytic activity during the process of photo-degradation of formaldehyde and some TVOC gases under visible light irradiation.     

Microstructure of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> hybrid electrospun nanofibers and their application in dye degradation

SiO₂/TiO₂ hybrid nanofibers were prepared by electrospinning and applied for photocatalytic degradation of methylene blue (MB). The phase structure, specific surface area, and surface morphologies of the SiO₂/TiO₂ hybrid nanofibers were characterized through thermogravimetry (TG), X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), etc. XRD measurements indicated that doping of silica into TiO₂ nanofibers can delay the phase transition from anatase to rutile and decrease the grain size. SEM and BET characterization proved that silica doping can remarkably enhance the porosity of the SiO₂/TiO₂ hybrid nanofibers. The MB adsorption capacity and photocatalytic activity of the SiO₂/TiO₂ hybrid nanofibers were distinguished experimentally. It was found that, although increased silica doping content could enhance the MB adsorption capacity, the intrinsic photocatalytic activity gradually dropped. The SiO₂ (10 %)/TiO₂ composite nanofibers exhibited the highest MB degradation rate, being superior to SiO₂ (20 %)/TiO₂ or pure TiO₂.     

Preparation of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles by mechanical alloying and annealing for sensitizing C-modified TiO<Subscript>2</Subscript> and acquirement of efficient photocatalyst

ZnFe₂O₄ nanoparticles sensitized by C-modified TiO₂ hybrids (ZnFe₂O₄–TiO₂/C) were successfully prepared by a feasible method. The ZnFe₂O₄ nanoparticles were prepared by mechanical alloying and annealing. The residual organic compounds in the synthetic process of TiO₂ were selected as the carbon source. The as-prepared composites were characterized by X-ray diffraction, Raman spectroscopy, X-ray fluorescence, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible light diffuse reflectance spectroscopy (UV–Vis) and N₂ adsorption–desorption analysis. The photocatalytic activity of the photocatalysts was measured by degradation of methyl orange under ultraviolet (UV) light and simulated solar irradiation, respectively. The results show that the carbon did not enter the TiO₂ lattice but adhered to the surface of TiO₂. The photocatalytic activity of the as-prepared C-modified TiO₂ (TiO₂/C) improved both under UV and simulated solar light irradiation, but the improvement was not dramatic. Introduction of ZnFe₂O₄ into the TiO₂/C could enhance the absorption spectrum range. The ZnFe₂O₄–TiO₂/C hybrids exhibited a higher photocatalytic activity both than that of the pure TiO₂ and TiO₂/C under either UV or simulated solar light irradiation. The complex synergistic effect plays an important role in improving the photocatalytic performance of ZnFe₂O₄–TiO₂/C composites. The optimum photocatalytic performance was obtained from the ZnFe₂O₄(0.8 wt%)–TiO₂/C sample.     

Synthesis,Adsorptive, and Photocatalytic Properties of Carbon Nanotubes/TiO<Subscript>2</Subscript> Nanocomposite Photocatalysts

The carbon nanotubes/TiO₂ (CNTs/TiO₂) composite photocatalysts composed of TiO₂ nanoparticles and multiwalled carbon nanotubes (CNTs) were prepared by a facile hydrothermal method. The photocatalysts were characterized by a range of analytical techniques including X-ray powder diffraction, field emission scanning electron microscope, thermal gravimetric analysis and UV–Vis optical absorption spectra, etc. The amount of TiO₂ nanoparticles growing on CNTs could be tuned by adjusting the dosage of precursor in the reaction solution. Both the adsorptivity and photocatalytic activities of pure CNTs, pure TiO₂, and the CNTs/TiO₂ nanocomposites were tested by the removal of methylene blue from water in dark and under a simulated sunlight, respectively. By comparison, the improved photocatalytic activity of the CNTs/TiO₂ nanocomposite is mainly due to that the CNTs can disperse the active component of TiO₂ nanoparticles, provide a larger the specific surface area, as well as act as an electron sink to accelerate the separation of the photogenerated charges.     

A P/N type compounded Cu<Subscript>2</Subscript>O/TiO<Subscript>2</Subscript> photo-catalytic membrane for organic pollutant degradation

A heterojunction thin film consisting of n-type titanium dioxide (TiO₂) and p-type cuprous oxide (Cu₂O) was fabricated on an FTO conducting glass. The TiO₂ films were grown on the FTO glass by sol–gel and spray pyrolysis methods, and Cu₂O was deposited on it via the hydrothermal method. The morphology, crystalline structure, and optical absorption characteristics were studied by scanning electron microscopy, X-ray diffraction, and ultraviolet–visible diffuse reflectance spectrum, respectively. The results show that the surface of the Cu₂O/TiO₂ film was composed of net and large grains, which contributed to a large specific surface area. The crystal phase of the TiO₂ in the Cu₂O/TiO₂ film remained anatase. The crystal phase of the Cu₂O could not be detected as it is found in traces. The Cu₂O/TiO₂ film had a stronger optical absorption ability than the pure TiO₂ film. To investigate catalytic activity, a photocatalytic degradation experiment of the Cu₂O/TiO₂ film was performed in a homemade thin-layer micro-reactor. The photocatalytic degradation of methylene blue increased with increasing amounts of deposited Cu₂O until a maximum limit was reached. The photocatalytic activity might have declined with an increase in Cu₂O content. The metallic oxide has the potential to screen other photocatalysts from the UV source.     

Synthesis of TiO<Subscript>2</Subscript> nano powder by the sol-gel method and its use as a photocatalyst

In this work the titanium dioxide powder was prepared by the optimized and simple Sol-Gel method and then characterized. The gelling pH was set to values of 3 (TiO₂-A), 7 (TiO₂-N) and 9 (TiO₂-B) to observe the effect on the properties of the material. In these three cases nanoparticulated materials were obtained with particle sizes between 10nm and 20nm. The larger surface areas were obtained at pH 3, which is several times larger than the others. Furthermore, with the gelling condition pH 3, it was possible to synthesize pure anatase phase titania. Some preliminary results on the test of the photocatalytic activity of the synthesized materials in the reduction of nitric oxide are presented. Based on these results the nanoparticle TiO2, which was prepared in acidic pH 3 with the pure anatase phase and the lowest particle size has the highest reactivity for the photocatalytic reduction of nitric oxide.     

Nanosized TiO<Subscript>2</Subscript> particles decorated on SiO<Subscript>2</Subscript> spheres (TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>): synthesis and photocatalytic activities

Nanosized TiO₂ and nano-anatase TiO₂ decorated on SiO₂ spherical core shells were synthesized by using a sol–gel method. The synthesized pure TiO₂ nano particle and TiO₂ grafted on SiO₂ sphere with various ratios have been characterized for their structure and morphologies by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrophotometry (FTIR) and transmission electron microscopy (TEM). Their surface areas were measured using the BET method. The photocatalytic activity of all nanocomposites was investigated using methylene blue as a model pollutant. The synthesized TiO₂/SiO₂ particles appeared to be more efficient in the degradation of methylene blue pollutant, as compared to pure TiO₂ particles.     

Photocatalytic intercalated material based on HLaNb<Subscript>2</Subscript>O<Subscript>7</Subscript> as host and Cd<Subscript>0.8</Subscript>Zn<Subscript>0.2</Subscript>S as guest

A novel photocatalytic material (Pt,Cd0.8Zn0.2S)/HLaNb2O7 was fabricated by successive intercalation and exchange reactions. The (Pt,Cd0.8Zn0.2S)/HLaNb2O7 possessed a gallery height less than 0.5 nm and showed a broad absorption with wavelength over 370-500 nm. Using (Pt,Cd0.8Zn0.2S)/HLaNb2O7 as catalyst, the photocatalytic H2 evolution was more than 160 cm3·h-1·g-1 in the presence of Na2S as a sacrificial agent under irradiation with wavelength more than 290 nm from a 100-W mercury lamp. Furthermore, the catalyst showed photocatalytic activity even under visible light irradiation.     

Preparation and photocatalytic activity of TiO<Subscript>2</Subscript> films with Ni nanoparticles

Titania thin films were synthesized by sol–gel dip-coating method with metallic Ni nanoparticles synthesized separately from an organometallic precursor Ni(COD)₂ (COD = cycloocta-1,5-diene) in presence of 1,3-diaminopropane as a stabilizer. Titania was obtained from a titanium isopropoxide precursor solution in presence of acetic acid. A Ni/TiO₂ sol system was used to coat glass substrate spheres (6, 4 and 3 mm diameter sizes), and further heat treatment at 400 °C was carried out to promote the crystallization of titania. XRD analysis of the TiO₂ films revealed the crystallization of the anatase phase. Transmission Electron Microscopy (TEM) and High Resolution TEM studies of Ni nanoparticles before mixing with the TiO₂ solution revealed the formation of Ni nanostructures with an average size of 5–10 nm. High-angle annular dark-field images of the Ni/TiO₂ system revealed well-dispersed Ni nanoparticles supported on TiO₂ and confirmed by AFM analysis. The photocatalytic activity of the Ni/TiO₂ films was evaluated in hydrogen evolution from the decomposition of ethanol using a mercury lamp for UV light irradiation. Titania films in presence of Ni nanoparticles show higher efficiency in their photocatalytic properties in comparison with TiO₂.     

Low temperature synthesis of nanosized ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript> photocatalysts by a citrate complex method

Nanosized ZnNb₂O₆ photocatalysts (band gaps ~4.0 eV) were successfully synthesized via a citrate complex method. Their particle sizes ranged from 50 to 150 nm. The result of Mott–Schottky measurement revealed that the flat-band potential of ZnNb₂O₆ was ca. −1.3 V versus Ag/AgCl at pH 6.6. The photocatalytic activities of the samples for the degradation of methyl orange were evaluated under UV-light (λ = 254 nm). It was found that the sample obtained at 850 °C showed the highest photocatalytic activity due to its opportune crystallinity and surface area. Furthermore, ·OH radicals were detected as the major oxidation agents responsible for the decomposition of methyl orange.     

Graphitic-C<Subscript>3</Subscript>N<Subscript>4</Subscript> quantum dots decorated {001}-faceted TiO<Subscript>2</Subscript> nanosheets as a 0D/2D composite with enhanced solar photocatalytic activity

Zero-dimensional (0D)/two-dimensional (2D) heterojunctions have attracted great attention in photocatalysis due to their superior interfacial effects. In this work, 0D g-C₃N₄ quantum dots (CNQDs) were firstly used to modify {001}-faceted 2D TiO₂ nanosheets by a simple solvothermal method. During the controlled growth of TiO₂ nanosheets with exposed reactive {001} facets, the CNQDs can be simultaneously assembled on the surface of TiO₂ nanosheets in a highly dispersive way. The 0D/2D composite containing only 0.5% of CNQDs shows the optimized solar photocatalytic activity for the degradation of rhodamine B and 4-chlorophenol. More importantly, the 0D/2D composite exhibits a better solar photocatalytic activity than the bulk g-C₃N₄/TiO₂ nanosheets composite. This improvement can be ascribed to the close interfacial contact and strong interaction between the highly dispersed CNQDs and the TiO₂ nanosheets, which could lead to efficient separation of the photogenerated electron–hole pairs, provide more catalytic active sites, and enhance the absorption of solar light. The 0D/2D composite also shows good stability for its practical applications.     

N,B, Si-tridoped mesoporous TiO<Subscript>2</Subscript> with high surface area and excellent visible-light photocatalytic activity

N, B, Si-tridoped mesoporous TiO₂, together with N-doped, N, B-codoped and N, Si-codoped TiO₂, was prepared by a modified sol–gel method. The samples were characterized by wide-angle X-ray diffraction (WAXRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, UV–visible adsorbance spectra (UV–vis) and X-ray photoelectron spectra (XPS). The N, B, Si-tridoped mesoporous TiO₂ showed small crystallite size, large specific surface area (350 m²/g), uniform pore distribution (3.2 nm) and strong absorption in the visible light region. The photocatalytic activities of the samples were evaluated by the photodegradation of 2,4-dichlorophenol (2,4-DCP) aqueous solution. The N, B, Si-tridoping sample exhibited much higher photocatalytic activity compared with other synthesized photocatalysts. The high activity could be attributed to the strong absorption in the visible light region, large specific surface area, small crystallite size, large amount of surface hydroxyl groups, and mesoporosity.     

Influence of ThO<Subscript>2</Subscript> on the photocatalytic activity of TiO<Subscript>2</Subscript>

Microcomposites consisting of TiO₂ (or Ce-doped TiO₂) and ThO₂ (0.5–2% of the TiO₂ mass) are produced by sol-gel synthesis of TiO₂ in presence of ThO₂. X-ray diffraction study reveals the effects of ThO₂ (compared to the ThO₂-free TiO₂, obtained by the same method) on the anatase interplanar distances, crystallites size and phase composition. The photocatalytic tests in presence of the composites under UV irradiation reveal an increase of the Malachite Green degradation rate constant. The effect depends on the Th relative content, temperature of annealing of the catalyst and addition of other doping agent. The highest photocatalytic activity is observed for TiO₂ obtained at 550°C and containing 1% ThO₂. The composite exhibits activity in dark, also. The presence of Ce⁴⁺ ions is not an obligatory requirement for the realization of the ThO₂ effect. The reported results suggest that the radioactivity of the Th and/or its decay products is one of the main factors responsible for the increased photocatalytic activity of TiO₂.