Preparation and characterization of highly photoactive nanocrystalline TiO<Subscript>2</Subscript> powders by solvent evaporationinduced crystallization method

Highly photoactive bi-phase nanocrystalline TiO₂ photocatalyst was prepared by a solvent evaporation-induced crystallization (SEIC) method, and calcined at different temperatures. The obtained TiO₂ photocatalyst was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air. The results show that solvent evaporation can promote the crystallization and phase transformation of TiO₂ at 100°C. When calcination temperatures are below 600°C, the prepared TiO₂ powders show bimodal pore size distributions in the mesoporous region. At 700°C, the pore size distributions exhibit monomodal distribution of the inter-aggregated pores due to the collapse of the intra-aggregated pores. At 100°C, the obtained TiO₂ photocatalyst by this method shows good photocatalytic activity, and at 400°C, its photocatalytic activity exceeds that of Degussa P25. This may be attributed to the fact that the prepared TiO₂ photocatalyst has higher specific surface areas, smaller crystallite size and bimodal pore size distribution.     

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.     

Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Effects of urea on the microstructure and photocatalytic activity of bimodal mesoporous titania microspheres

Bimodal mesoporous TiO₂ microspheres with high photocatalytic activity were prepared by a hydrothermal method using titanium sulfate as precursor in the presence of urea. The results indicate that all prepared samples show bimodal pore-size distributions in the mesoporous region: smaller intra-aggregated pores with peak pore diameter of ca. 2 nm and larger inter-aggregated pores with peak pore diameter of ca. 12.5 nm. The molar ratio of urea to Ti(SO₄)₂ (R_u) has an obvious influence on the morphology, microstructure and photocatalytic activity of TiO₂. With increasing R_u, specific surface areas and porosity increase, contrarily, the crystallite size and relative anatase crystallinity decrease. The photocatalytic activity first increases with R_u. At R_u = 2.0, the photocatalytic activity reaches the highest and is obviously higher than that of Degussa P25. With further increasing R_u, the photocatalytic activity decreases. The formation rate of hydroxyl radicals during photocatalysis has a positive correlation with the photocatalytic activity.     

Synthesis of Fe<Superscript>3+</Superscript> doped ordered mesoporous TiO<Subscript>2</Subscript> with enhanced visible light photocatalytic activity and highly crystallized anatase wall

Fe³⁺ doped mesoporous TiO₂ with ordered mesoporous structure were successfully prepared by the solvent evaporation-induced self-assembly process using P123 as soft template. The properties and structure of Fe³⁺ doped mesoporous TiO₂ were characterized by means of XRD, EPR, BET, TEM, and UV–vis absorption spectra. The characteristic results clearly show that the amount of Fe³⁺ dopant affects the mesoporous structure as well as the visible light absorption of the catalysts. The photocatalytic activity of the prepared mesoporous TiO₂ was evaluated from an analysis of the photodegradation of methyl orange under visible light irradiation. The results indicate that the sample of 0.50%Fe–MTiO₂ exhibits the highest visible light photocatalytic activity compared with other catalysts.     

Solvothermal preparation of copper(II) porphyrin-sensitized mesoporous TiO<Subscript>2</Subscript> composites: enhanced photocatalytic activity and stability in degradation of 4-nitrophenol

Four new copper(II) porphyrins CuPp(1, 2, 3, 4) with a different number of peripheral ester groups were synthesized and used to sensitize the mesoporous TiO₂ under solvothermal condition, and accordingly, four mesoporous CuPp(1, 2, 3, 4)/TiO₂ composites were obtained. These composites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, BET nitrogen adsorption–desorption isotherms (BET), UV–vis diffuse reflectance spectroscopy (UV–vis-DRS), and Fourier-transform infrared spectroscopy (FT-IR). The results showed the crystal structure and morphology of mesoporous TiO₂ were not affected by the porphyrin existence on its surface. The photocatalysis properties of mesoporous TiO₂ and CuPp(1, 2, 3, 4)/TiO₂ have been evaluated by conducting the photocatalytic degradation of 4-nitrophenol (4-NP) under visible-light irradiation, and the result showed their higher photocatalytic activities and the order is: CuPp(4)/TiO₂ > CuPp(3)/TiO₂ > CuPp(2)/TiO₂ > CuPp(1)/TiO₂ ? TiO₂. The probable reasons are their large surface area and different number of peripheral groups in CuPp, which separate electron–hole pairs efficiently. The repetition test of CuPp(1, 2, 3, 4)/TiO₂ composites demonstrated that they still maintained superior photocatalytic activity over six recycles.     

Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites

Na⁺ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m²/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO₂ samples prepared were found to have photocatalytic activity in Cu^II, Ni^II and Ag^I reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO₂ Degussa P25.The effects of the thermal treatment of mesoporous TiO₂ upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO₂/Ag⁰ to TiO₂/Ni⁰ to TiO₂/Cu⁰ was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites.     

Solar photocatalytic activities of porous Nb-doped TiO2 microspheres prepared by ultrasonic spray pyrolysis

Ultrasonic spray pyrolysis method was used to prepare Nb-doped TiO₂ porous microspheres with an average diameter of 500 nm for solar photocatalytic applications. The effect of Nb-doping on morphology, structure, surface area, as well as spectral absorption properties of TiO₂ microspheres was investigated with SEM, TEM, XRD, Raman spectra, BET, and UV-Vis absorption spectra. The Nb-doping decreased the grain size of TiO₂ porous microsphere, and influenced its surface area and pore size distribution dependent on the doping concentration, but changed negligibly the morphology and size of TiO₂ microspheres. Moreover, the Nb-doping was observed to extend the spectral absorption of TiO₂ into visible spectrum, and the absorption onset was red-shifted for about 88 nm at a doping level of 5% compared to pristine TiO₂ microspheres. Under solar or visible irradiation, Nb-doped TiO₂ microspheres showed higher photocatalytic activity for methylene blue degradation compared with TiO₂ microspheres, which could be ascribed to the extended light absorption range and the suppression of electron-hole pair recombination.     

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.     

Defect induced nickel,nitrogen-codoped mesoporous TiO2 microspheres with enhanced visible light photocatalytic activity

Nickel, nitrogen-codoped mesoporous TiO₂ microspheres (Ni–N–TiO₂) with high surface area, and an effective direct band gap energy of ∼2.58 eV. Nickel sulfate used as the Ni source and ammonia gas as the N source here. The efficiency of the as-prepared samples was investigated by monitoring the degradation of Rhodamine B under visible light irradiation. The experimental results indicate that Ni-doped mesoporous TiO₂ microspheres show higher photocatalytic activity than mesoporous TiO₂ microspheres under visible light irradiation. It mainly due to that the electron trap level (Ni²⁺/Ni⁺) promoting the separation of charge carriers and the oxygen vacancies inducing the visible light absorption. In addition, Ni–N–TiO₂ shows enhanced activity compared with Ni–TiO₂. Codopants and dopants are found to be uniformly distributed in TiO₂ matrix. Among the all samples the 0.5% molar quantity of Ni dopant and 500 °C 2 h nitriding condition gives the highest photocatalytic activity. The treatment of ammonia gas on Ni–TiO₂ sample induced oxygen vancancies, substitutional and interstitial N. A suitable treatment by ammonia gas also promote separation of charge carriers and the absorption of visible light. The active species generated in the photocatalytic system were also investigated. The strategy presented here gives a promising route towards the development of a metal and non-metal codoped semiconductor materials for applied photocatalysis and related applications.     

Photocatalytic production of hydrogen from water–alcohol media with the participation of mesoporous TiO<Subscript>2</Subscript>

Samples of mesoporous TiO₂ containing 80-85% of anatase and 15-20% of rutile with average particle and pore sizes of ∼10 nm and specific surface areas of 70 m²/g were obtained. The nanohetero structures TiO₂/Cu formed during photocatalytic reduction of Cu^II exhibit photocatalytic activity in the release of hydrogen from water–ethanol mixtures. The quantum yield with respect to atomic hydrogen amounts to 1.5.     

Influence of NH<Subscript>3</Subscript>-treating temperature on visible light photocatalytic activity of N-doped P<Subscript>25</Subscript>-TiO<Subscript>2</Subscript>

The influence of NH₃-treating temperature on the visible light photocatalytic activity of N-doped P₂₅-TiO₂ as well as the relationship between the surface composition structure of TiO₂ and its visible light photocatalytic activity were investigated. The results showed that N-doped P₂₅-TiO₂ treated at 600°C had the highest activity. The structure of P₂₅-TiO₂ was converted from anatase to rutile at 700°C. Moreover, no N-doping was detected at the surface of P₂₅-TiO₂. There was no simply linear relationship between the visible light photocatalytic activity and the concentration of doped nitrogen, and visible light absorption. The visible light photocatalytic activity of N-doped P₂₅-TiO₂ was mainly influenced by the synergistic action of the following factors: (i) the formation of the single-electron-trapped oxygen vacancies (denoted as V_o^·); (ii) the doped nitrogen on the surface of TiO₂; (iii) the anatase TiO₂ structure.     

Preparation,Characterization and Photocatalytic Activity of Lanthanum Doped Mesoporous Titanium Dioxide

Lanthanum doped mesoporous titanium dioxide photocatalysts with different La content were synthesized by template method using tetrabutyltitanate (Ti(OC₄H₉)₄) as precursor and Pluronic P123 as template. The catalysts were characterized by thermogravimetric dif-ferential thermal analysis, N₂ adsorption-desorption measurements, X-ray diffraction, and UV-Vis adsorption spectroscopy. The effect of La³⁺ doping concentration from 0.1% to 1% on the photocatalytic activity of mesoporous TiO₂ was investigated. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of about 10 nm with high surface area of 165 m²/g. X-ray photoelectron spectroscopy measurements in-dicated the presence of C in the doped samples in addition to La. Compared with pure mesoporous TiO₂, the La-doped samples extended the photoabsorption edge into the visible light region. The results of phenol photodecomposition showed that La-doped mesoporous TiO₂ exhibited higher photocatalytic activities than pure mesoporous TiO₂ under UV and visible light irradiation.     

Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO₂ microspheres was developed. Formation of mesoporous TiO₂ and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO₂ microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO₂ microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide.     

Development of mesoporous TiO2 microspheres with high specific surface area for selective enrichment of phosphopeptides by mass spectrometric analysis

In this study, mesoporous TiO₂ microspheres were synthesized by simple hydrothermal reaction, and successfully developed for phosphopeptides enrichment from both standard protein digestion and real biological sample such as rat brain tissue extract. The mesoporous TiO₂ microspheres (the diameter size of about 1.0 μm) obtained by simple hydrothermal method were found to have a specific surface area of 84.98 m²/g, which is much larger than smooth TiO₂ microspheres with same size. The surface area of mesoporous TiO₂ microspheres is almost two times of commercial TiO₂ nanoparticle (a diameter of 90 nm). Using standard proteins digestion and real biological samples, the superior selectivity and capacity of mesoporous TiO₂ microspheres for the enrichment of phosphorylated peptides than that of commercial TiO₂ nanoparticles and TiO₂ microspheres was also observed. It has been demonstrated that mesoporous TiO₂ microspheres have powerful potential for selective enrichment of phosphorylated peptides. Moreover, the preparation of the mesoporous TiO₂ microspheres obtained by the hydrothermal reaction is easy, simple and low-cost. These mesoporous TiO₂ microspheres with the ability of large scale synthesis can widely be applied for phosphorylated proteomic research.     

Preparation and characterization of SiO2/TiO2 composite microspheres with microporous SiO2 core/mesoporous TiO2 shell

SiO₂/TiO₂ composite microspheres with microporous SiO₂ core/mesoporous TiO₂ shell structures were prepared by hydrolysis of titanium tetrabutylorthotitanate (TTBT) in the presence of microporous silica microspheres using hydroxypropyl cellulose (HPC) as a surface esterification agent and porous template, and then dried and calcined at different temperatures. The as-prepared products were characterized with differential thermal analysis and thermogravimetric (DTA/TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption. The results showed that composite particles were about 1.8 μm in diameter, and had a spherical morphology and a narrow size distribution. Uniform mesoporous titania coatings on the surfaces of microporous silica microspheres could be obtained by adjusting the HPC concentration to an optimal concentration of about 3.2 mmol L⁻¹. The anatase and rutile phase in the SiO₂/TiO₂ composite microspheres began to form at 700 and 900 °C, respectively. At 700 °C, the specific surface area and pore volume of the SiO₂/TiO₂ composite microspheres were 552 and 0.652 mL g⁻¹, respectively. However, at 900 °C, the specific surface area and pore volume significantly decreased due to the phase transformation from anatase to rutile.     

Chitosan-modified TiO<Subscript>2</Subscript> as photocatalyst for ethanol reforming under visible light

This work reports the reforming of bio-ethanol on chitosan–TiO₂ hybrid photocatalysts at ambient temperature. The influence of chitosan composition on the photocatalytic performance of chitosan–TiO₂ hybrid was studied. The hybrids were characterized by CHN elemental analysis, nitrogen adsorption–desorption isotherms, thermogravimetric analysis, diffuse reflectance spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results showed that the preparation variables used for the incorporation of chitosan on TiO₂ promoted changes in the morphology, superficial area, crystal size and porosity of the photocatalyst, affecting the band gap of this semiconductor and consequently the reactivity of the chitosan–TiO₂ hybrids. The catalysts were evaluated for hydrogen production from ethanol under visible light. It was demonstrated that the calcination temperature of 623 K and a chitosan content of 20% were the most appropriate preparation conditions and the resulting product displays a pore size of 1.9 nm, crystal size of 11.3 nm, BET area of 178 m² g^?1 and band gap of 2.92 eV. The calcination temperature of 623 K and incorporation of 20% of chitosan obtained the same results in the conversion rate of hydrogen in comparison to the pure TiO₂ P25.     

The effects of the nanostructure of mesoporous TiO<Subscript>2</Subscript> on optical band gap energy

Mesoporous TiO₂ is prepared by sol–gel process with a triblock copolymer as an organic template and aqueous TiOCl₂ solution as inorganic precursor. The XRD patterns reveal that only the anatase phase can be observed in mesoporous TiO₂, regardless of the different calcining temperatures, and with increasing calcining temperature the grain size gradually increases. The grain sizes of TiO₂ increased from 4.7 to 11.9 nm with calcining temperature increasing from 300 to 400 °C. The pore size and the surface area evaluated from the Barrett–Joyner–Halenda model and Brunauer–Emmett–Teller method indicated that the average pore sizes increased from 87 to 153 Å and specific surface areas decreased from 179.71 to 74.31 m²/g for 300–400 °C calcination. The relationship between the optical band gap (E _g) and microstructure of anatase has been determined and discussed. The quantum confinement effect is observed at grain sizes lower than 10 nm, and the estimated E _g shifts from 3.32 to 3.46 eV. These results suggest that there are potential applications of mesostructured TiO₂ with nanocrystals in the design of optical devices and photocatalysts.     

Photocatalytic degradation of organic compounds in aqueous systems by Fe and Ho codoped TiO<Subscript>2</Subscript>

Undoped, single-doped, and codoped TiO₂ nanoparticles were prepared by the sol-gel method and characterized with X-ray diffraction (XRD), the Brunauer-Emmett-Teller (BET)-specific surface area (S_BET), UV-Vis absorption spectra (UV-Vis), and X-ray photoelectron spectroscopy (XPS). Their photocatalytic activity was evaluated by methyl orange (MO) degradation in an aqueous suspension under UV or simulated solar light illumination. XRD showed that all samples calcined at 600°C preserved the anatase structure, and doping inhibited the increase of crystallite size. The BET result revealed that doping improved the surface area of TiO₂. UV-Vis indicated that Fe³⁺-doping broadened the absorption profile of TiO₂. XPS demonstrated that doping was advantageous to absorb more surface hydroxyl groups or chemisorbed water molecules. Photocatalytic degradation showed that the photocatalytic activity of TiO₂ codoped with Fe³⁺ and Ho³⁺ ions was markedly improved. This was ascribed to the fact that there was a cooperative action in the two doped elements. Fe³⁺-doping broadens the absorption profile, improves photo utilization of TiO₂, and then generates more electronhole pairs. Ho³⁺-doping restrains the increase in grain size and retards the recombination of photo-generated electrons and holes.     

Rapid Synthesis of Mesoporous TiO2 for the Photoanodes in Dye Sensitized Solar Cells

Mesoporous TiO₂ microspheres with high specific surface areas were synthesized by means of a facile one‐step microwave hydrothermal process without using any template. The mesoporous materials were rapidly achieved using TiCl₄, urea and ammonium sulphate at comparatively low microwave power (400 W) for 8 min irradiation. The morphology and microstructure of the as‐prepared products were characterized by field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), transmission electron microscopy (TEM) and Brunauer‐Emmett‐Teller (BET) surface area analysis. Structural characterization indicates that the TiO₂ microspheres display mesoporous structure. The average pore sizes and BET surface areas of the spheres were 5.3 nm and 222 m²g^?1, respectively. The mesoporous nanocrystals synthesized at 160 °C for 8 min were then used to prepare the photoanode for dye sensitized solar cells (DSSCs). A high power conversion efficiency of 5.72% was achieved from the mesoporous TiO₂ based photoanode, representing about 25.7% improvement over the efficiency of P25 photoanode.