Synthesis and photocatalytic activity of ring-like anatase TiO2 with {001} facts exposed

Developing photocatalysts with specific morphology and good photocatalytic activities promises good opportunities to discover the geometry-dependent properties. In the present work, ring-like anatase TiO₂ with dominant {001} facets exposed were successfully synthesized via a one-pot solvothermal process of tetrabutyl titanate and hydrofluoric acid solution at 180 °C for 8 h. We found that hydrofluoric acid plays an important role in the formation of ring-like TiO₂. The morphology and microstructure were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Brunauer–Emmett–Teller N₂ gas adsorption–desorption isotherms. The photocatalytic activity was evaluated by photocatalytic oxidation degradation of methylene blue aqueous solution under UV light. Results showed that ring-like TiO₂ with {001} facets exposed exhibited an excellent photocatalytic activities due to its unique structure: Nanosheets with hole.     

Hydrothermal synthesis and visible-light photocatalytic activity of α-Fe2O3/TiO2 composite hollow microspheres

Novel α-Fe₂O₃/TiO₂ composite hollow spheres were successfully synthesized by a template-assisted precipitation reaction using urea as a precipitating agent and carbon spheres as templates in a mixed solvent of water and ethanol, and then calcined at 400 °C for 4 h. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption isotherms, and vibrating sample magnetometer. The influence of calcination temperature and the molar ratio of titanium to iron (R) on the photocatalytic activity of the samples was investigated. The results indicated that the composite spheres show magnetic characteristics at room temperature and good photocatalytic activity under visible-light irradiation compare to the single-component α-Fe₂O₃ particles. This method can be further applied to synthesize nanocomposites of magnetic metal oxide and other metal oxide.     

Growth mechanism and photocatalytic activity of chrysanthemum-like anatase TiO2 nanostructures

Chrysanthemum-like hierarchical anatase TiO₂ nanostructures self-assembled by nanorods have been successfully fabricated by a simple solvothermal route without using template materials or structure-directing additives. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Raman spectrometer system (Raman), UV–vis absorption spectroscopy (UV–vis) and N₂ adsorption–desorption measurement. The results indicate that synthesized chrysanthemum-like hierarchical anatase TiO₂ nanostructures have a spherical shape with an average diameter of 1.5 μm and they are composed of nanorods with a width of about 30 nm and a length of about 300 nm. The pore distribution of the sample exhibits two kinds of pores. Such mesoporous structure of the sample might be extremely useful in photocatalysis because they possess efficient transport pathways to the interior and supplies higher specific area for more pollutant molecules to be absorbed. In addition, the synthesized TiO₂ nanostructures show enhanced photocatalytic activity compared with commercial P25 for the degradation of RhB under UV light irradiation, which can be attributed to their special hierarchical structure and high light-harvesting capacity.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Effect of carbon doping on WO3/TiO2 coupled oxide and its photocatalytic activity on diclofenac degradation

The improved photocatalyst carbon-doped WO₃/TiO₂ mixed oxide was synthesized in this study using the sol–gel method. The catalyst was thoroughly characterized by X-ray diffraction (XRD), diffuse reflectance UV–vis spectroscopy, N₂ adsorption desorption analysis, scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic efficiency of the prepared materials was evaluated with respect to the degradation of sodium diclofenac (DCF) in a batch reactor irradiated under simulated solar light. The progress of the degradation process of the drug was evaluated by high-performance liquid chromatography (HPLC), whereas mineralization was monitored by total organic carbon analysis (TOC) and ion chromatography (IC). The results of the photocatalytic evaluation indicated that the modified catalyst with tungsten and carbon (TWC) exhibited higher photocatalytic activity than TiO₂ (T) and WO₃/TiO₂ (TW) in the degradation and mineralization of diclofenac (TWC>TW>T). Complete degradation of diclofenac occurred at 250 kJ m⁻² of accumulated energy, whereas 82.4% mineralization at 400 kJ m⁻² was achieved using the photocatalytic system WO₃/TiO₂-C. The improvement in the photocatalytic activity was attributed to the synergistic effect between carbon and WO₃ incorporated into the TiO₂ structure.     

Hydrothermal synthesis of titanate nanostructures with high UV absorption characteristics

The titanate nanostructures with high UV absorption characteristics could be fabricated by hydrothermal method within a temperature range of 90–150 °C. TEM, XRD, BET analyses, and UV–vis spectroscopy were employed to elucidate the synthesized titanate nanostructure characteristics which were microstructure, phase transformation, specific surface area, and band gap energy, respectively. With an increase in the hydrothermal treating temperature from 90 to 120 °C, the specific surface area of titanate nanostructures was increased from 83 to 258 m²/g, while the band gap energy of titanate nanostructures was increased from 3.44 to 3.84 eV and then slightly decreased to 3.81 eV at 150 °C. The fabricated titanate nanostructures could exhibit higher UV adsorption capability but lower photocatalytic activity when compared with that of commercial TiO₂ powders.     

Morphology controlled hydrothermal synthesis and photocatalytic properties of ZnFe2O4 nanostructures

The present work is focused on studying morphology dependent catalysis of spinel ZnFe₂O₄ nanostructures. Different morphologies i.e. porous nanorods, nanoparticles, nanoflowers and hollow microspheres were designed hydrothermally. The as prepared nanomaterials were characterized using Fourier Transform Infra-Red (FTIR), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), Brunauer–Emmett–Teller (BET) technique and UV–visible spectrophotometer. The results confirmed formation of desired morphologies of cubic spinel ZnFe₂O₄ with high surface areas (92–138 m²/g) and narrow band gaps (1.76–1.97 eV). It suggested the use of ZnFe₂O₄ nanostructures as potential visible light photocatalysts. Therefore, the application of synthesized ZnFe₂O₄ nanostructures was studied in photo-Fenton degradation of dyes. The results indicated shape dependent relationship with photocatalytic activity as the degradation of dyes followed the order porous nanorods>nanoparticles>nanoflowers>hollow microspheres. The role of main active species in the reaction i.e. ^∙OH was also confirmed. All the materials exhibited stability and magnetic separability hence could act as potential photo-Fenton catalysts for wastewater treatment.     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Hydrothermal preparation of Ag-TiO2 nanostructures with exposed {001}/{101} facets for enhancing visible light photocatalytic activity

Nano-composite materials of Ag nanoparticles dispersed TiO₂ nanocubes with exposed {001}/{101} crystal faces were fabricated mainly via a flexible one-step method of hydrothermal treatment with different content of Ag from 1 up to 3 mol%. Prepared photocatalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. These analysis was carried out for understanding the contribution of different content of silver for enhancing the photocatalytic activity of TiO₂ nanocubes. Prepared silver nanoparticles had small particle size and grafted to the {101} crystal face of TiO₂ with the role of template control agent and linking agent. The photocatalytic performance of Ag-TiO₂ nanocubes were researched via Rhodamine B dye removal under visible light irradiation ( ≧420 nm). Ag-TiO₂ composite materials with the content of 2 mol% Ag showed the best photocatalytic activity for degradation of Rhodamine B, which was five times more than bare TiO₂ and associated with the localized surface plasmon resonance (LSPR) propelled effect. The mechanism by which silver enhanced the photocatalytic activity of TiO₂ was also demonstrated.     

Simple fabrication of thermally stable apertured N-doped TiO2 microtubes as a highly efficient photocatalyst under visible light irradiation

Apertured N-doped TiO₂ microtubes have been fabricated by simple hydrolysis of titania tetrachloride using ammonia without any external templates. The morphology and microstucture characteristics of apertured N-doped TiO₂ microtubes were characterized by means of the specific surface area (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transformed infrared (FT-IR), UV–visible diffuse reflectance spectra (DRS) and X-ray powder diffraction (XRD). The unique morphology of microtubes and mesoporous microstructure were maintained after a heat treatment at 723 K for 3 h, exhibiting significantly thermal stability. The catalysts exhibited high ultraviolet and visible light photocatalytic activity in degrading phenol and methyl orange.     

Photocatalytic hydrogen production from methanol aqueous solution under visible-light using Cu/S–TiO2 prepared by electroless plating method

Cu was loaded on the S-doped TiO₂ by electroless plating method. The prepared Cu/S–TiO₂ exhibited high photocatalytic activity for hydrogen generation, and the yield is up to 7.5 mmol h^− 1 g^− 1cat in methanol solution. Their physical structure and chemical properties were characterized by UV–Vis, XRD, XPS and EXAFS. The copper species were CuO and Cu₂O, and the sample showed excellent visible light absorption ability. Comparing with the sample prepared by chemical reducing method, the electroless plated copper on S–TiO₂ was highly dispersed, which could facilitate photo-generated charges capture, transfer and separation.     

Photocatalytic performance of Ru doped anatase mounted on silica for reduction of carbon dioxide

Ru doped anatase supported on silica was prepared by solid-state dispersion method and examined for the photocatalytic reduction of carbon dioxide in aqueous medium at ambient conditions. To assist in interpreting the photocatalytic behaviour of Ru-TiO₂/SiO₂, reference systems consisting of Ru doped TiO₂ and TiO₂ supported on SiO₂ were also analyzed and the conditions were optimized. Ru/TiO₂ photocatalysts with metal loadings of 0.1, 0.3, 0.5 and 1.0 wt% were prepared by impregnation method and a series of TiO₂/SiO₂ catalysts with low TiO₂ (1, 3, 5 and 10 wt%) contents were prepared by solid-state dispersion method. The photocatalysts were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis DRS, FT-IR and Raman spectroscopy. The results showed that TiO₂ particles with Ru ions have higher photocatalytic activity than undoped TiO₂ and the optimum Ru loading was found to be 0.5 wt%. Nevertheless, the yield increased notably when TiO₂ was supported on SiO₂. This strong enhancement suggests that in 10 wt% TiO₂/SiO₂ the efficiency of charge separation is strongly influenced through the presence of TiOSi bridging bonds. On the contrary, Ru-TiO₂/SiO₂ has no significant improvement in activity over TiO₂/SiO₂ except that it shows nearly quadruple times higher activity for the formation of methanol than Ru/TiO₂. The difference in the photocatalytic activity is related to its physico-chemical properties.     

Improved photo-catalytic activity of single-crystalline TiO2 nanowires surrounded by Pt cube nanoparticles

We report improved photo-catalytic properties of single-crystalline TiO₂ nanowires surrounded by Pt cubes for methanol electrooxidation under UV illumination. The TiO₂–Pt consists of single-crystalline TiO₂ nanowires grown along [0 0 1] direction and Pt cube nanoparticles with dominantly exposed {1 0 0} facets confirmed by transmission electron microscopy images and fast Fourier transform patterns. The nanostructure electrode consisting of TiO₂ nanowires and Pt cubes exhibits a remarkably improved performance for methanol electrooxidation in acid solution as compared to that of TiO₂ nanowires.     

Supercritical hydrothermal synthesis of titanium dioxide nanostructures with controlled phase and morphology

A novel template- and organic-free synthesis of TiO₂ nanostructures with controlled phase and morphology was realized through batch supercritical hydrothermal treatment (400 °C) of titanate nanotubes (TNTs) with H₂O₂ in NaOH aqueous solution. Well-defined 3D titanate hierarchical spheres (THSs), 2D multilayered titanate nanosheets (TNSs), and 1D monodisperse anatase nanorods (ANRs) exposing (0 1 0) facets were prepared in 15 min by slightly varying the NaOH solution pH. Specifically, the obtained Na/H-THSs (without/with HCl neutralization) exhibited highly porous structures with large specific surface area (109 m² g⁻¹ and 196 m² g⁻¹, respectively). Temperature-dependent phase and morphology evolutions of products under subcritical condition (200 and 300 °C) were investigated. The formation of the TiO₂ nanostructures from TNTs was proposed mainly following a dissolution–nucleation-growth mechanism, suggesting that both supercritical temperature and NaOH solution pH were determinant factors governing the nucleation and growth process and thus the phase and morphology.     

Thermodynamic parameters of activation for photodegradation of phenolics

The photocatalytic degradation of three phenolics namely phenol, 4-chlorophenol and 4-nitrophenol were carried out in aerated aqueous suspension of TiO₂ irradiated by ultraviolet light. The influence of temperature at optimized pH and TiO₂ concentration was studied. The degradation kinetics were somewhat accelerated by increase in temperature in the range 25–45 °C and apparent activation energy was calculated to be 9.68–21.44 kJ mol^?1. Thermodynamic parameters of activation were also assessed for the degradation process. Formation of acidic species results in decrease in pH of solution. The appearance and the evolution of main intermediate species like hydroquinone, benzoquinone and catechol during the degradation process were computed by UV–vis spectral analysis.     

Efficient hydrogen production by photocatalytic water-splitting using Pt-doped TiO2 hollow spheres under visible light

Pt doped TiO₂ hollow spheres (Pt/HS-TiO₂) are prepared by a sol–gel method and characterized by XRD, SEM, TEM and UV-visible absorption spectra. In addition, Pt/HS-TiO₂ is employed as the catalyst for photocatalytic hydrogen production from water splitting under visible light irradiation. The results show that Pt/HS-TiO₂ with hollow sphere structure presents excellent photocatalytic hydrogen evolution performance. The hydrogen generation rate can reach more than 1023.71 μmol h⁻¹ g⁻¹ at room temperature and no obvious deactivation is observed after 30 h irradiation. Furthermore, the reactively of Pt/HS-TiO₂ could be reproduced in the repeated cycle. Therefore, Pt/HS-TiO₂ is a promising photocatalyst to efficiently generate hydrogen under visible-light irradiation at room temperature.     

Preparation of oriented SiO32− doped TiO2 film and degradation of methylene blue under visible light irradiation

SiO₃^2? doped TiO₂ films with oriented nanoneedle and nanorectangle block structure has been firstly synthesized by hydrothermal synthesis method. The prepared samples are characterized, X-ray diffraction (XRD) results demonstrate that the SiO₃^2? doped TiO₂ films are rutile and brookite phases. The scanning electron microscope (SEM) analysis reveals that the quantity of O₂ affects the morphology of the SiO₃^2? doped TiO₂ films (SiTiA films prepared with unmodified substrate). The SiO₃^2? doped TiO₂ films (SiTiB films prepared with modified substrate) display two layers, one is porous structure, the other is nanoneedle structure. UV–vis, IR, transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) microscopy all prove that SiO₃^2? have been doped in the TiO₂ crystal structure. They have remarkable red shift and higher photocatalytic activity of degradation of methylene blue than P-25 under visible light (λ > 420 nm) irradiation. Besides, photocatalytic activity of the film is stable during 4 times recycling.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

A novel TiO2 − xNx/BN composite photocatalyst: Synthesis,characterization and enhanced photocatalytic activity for Rhodamine B degradation under visible light

A novel TiO_2 − xN_x/BN composite photocatalyst was prepared via a facile method using melamine–boron acid adducts (M·2B) and tetrabutyl titanate as reactants. The morphological results confirmed that nitrogen-doped TiO₂ nanoparticles were uniformly coated on the surface of porous BN fibers. A red shift of absorption edge from 400 nm (pure TiO₂) to 520 nm (TiO_2 − xN_x/BN composites) was observed in their UV–Vis light absorption spectra. The TiO_2 − xN_x/BN photocatalysts exhibited enhanced photocatalytic activity for the degradation of Rhodamine B (RhB) and the highest photocatalytic degradation efficiency reached 97.8% under visible light irradiation for 40 min. The mechanism of enhanced photocatalytic activity was finally proposed.     

Iridium,carbon and nitrogen multiple-doped TiO2 Nanoparticles with enhanced photocatalytic activity

The aim of this research is to enhance the photocatalytic activity of TiO₂ nanoparticles for the UV–visible light by multiple-doping with Iridium, carbon and nitrogen. The tridoped TiO₂ photocatalyst were prepared by wet chemical method, and characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible light diffuse reflection spectroscopy and room temperature photoluminescence spectroscopy. Besides, the photocatalytic H₂ evolution performance of Ir-C-N tridoped TiO₂ under UV–visible light irradiation was evaluated. It was found that Ir existed as Ir⁴⁺ by substituting Ti in the lattice of TiO₂; meanwhile, C and N were also incorporated into the surface of TiO₂ nanoparticles in interstitial mode. Meanwhile, Ir-C-N tridoping extended the absorption of TiO₂ into the visible light region and narrowed its band gap to ~3.0 eV, resulting in enhanced photocatalytic H₂ evolution under UV–visible light irradiation. This could be attributed to narrow band gap and proper electronic structure of TiO₂ after Ir-C-N tridoping.