Synthesis of a magnetically separable composite photocatalyst with high photocatalytic activity under sunlight

A novel magnetically separable composite photocatalyst (N-doped titania-coated γ-Fe₂O₃ magnetic activated carbon) was prepared. It consists of N-doped titania, activated carbon and γ-Fe₂O₃. The whole processes were carried out under low temperature. The prepared sample was characterized by XRD, DRS, SEM, BET and vibrating sample magnetometer (VSM). The photocatalytic activity was determined by degradation of Reactive Brilliant Red X-3B in an aqueous solution under solar irradiation. Results showed that this as-prepared composite photocatalyst exhibited much higher photocatalytic activity than Degussa P25. Furthermore, the photocatalyst can be separated easily by an external magnetic field. Thus, the photocatalyst can be recycled without mass losing, and the degradation percent of X-3B decreased less than 2% after six cycles.     

A one-pot method to prepare N-doped titania hollow spheres with high photocatalytic activity under visible light

N-doped titania hollow spheres (NTHS) were prepared by a one-pot hydrothermal method using urea as precursor of nitrogen. The prepared hollow spheres were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectrum (DRS). The photocatalytic activity of as-prepared titania hollow spheres was determined by degradation of Reactive Brilliant Red dye X-3B (C.I. reactive red 2) under visible light irradiation, and was compared to non-doped titania hollow spheres and commercial P25 titania. Results indicated that the as-prepared NTHS showed highest photocatalytic activity.     

Synthesis of fluorine-doped titania-coated activated carbon under low temperature with high photocatalytic activity under visible light

Fluorine-doped anatase titania sols were synthesized by hydrolysis of titanium-n-butoxide in the presence of abundant acidic aqueous solution and using ammonium fluoride as fluorine precursors, under mild condition. The prepared fluorine-doped titania nanoparticles were loaded on activated carbon in a rotatory evaporator under vacuum to form a composite photocatalyst. X-ray diffraction, Fourier transform infrared spectrum analysis, UV-visible spectroscopy, scanning electron microscope and Brunauer-Emmett-Teller adsorption measurement were used to characterize these as-prepared powders. The photocatalytic activity of the sample was evaluated by degrading phenol under visible light. Results showed that the composite photocatalyst was porous due to its nano-microstructure. The number of hydroxyl groups on the titania surface was enhanced after fluorine doping. Compared with pure titania-activated carbon and Degussa P25, the as-prepared composite powders exhibited much higher photocatalytic activity, although absorption response range into the visible region was not detected by diffuse reflection spectra.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Hydrothermal synthesis of well-dispersed ultrafine N-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light

Ultrafine nitrogen-doped TiO₂ nanoparticles with narrow particle size distribution, good dispersion, and high surface area were synthesized in the presence of urea and PEG-4000 via a hydrothermal procedure. TEM observation, N₂ adsorption, XRD, UV-vis spectroscopy, the Raman spectroscopy and XPS analysis were conducted to characterize the synthesized TiO₂ particles. The synthesized TiO₂ particles were a mixture of 49.5% anatase and 50.5% rutile with a size of around 5 nm. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive Brilliant Blue KN-R under both UV and visible light. The synthesized TiO₂ particles showed much higher photocatalytic activity than a commercial P25 TiO₂ powder under both UV and visible light irradiations. The high performance is associated to N doping, the reduced particle size, good dispersion, high surface area, and a quantum size effect.     

Visible-light-driven titania photocatalyst co-doped with nitrogen and ferrum

Nitrogen and ferrum co-doped titania photocatalyst was prepared by the sol-gel route. The prepared photocatalyst was characterized by various techniques including X-ray diffraction (XRD), UV-vis diffusive reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and N₂ adsorption-desorption isotherm. The photocatalytic activity of the co-doped titania photocatalyst was evaluated by the degradation of methyl orange (MO) from aqueous solution under visible light irradiation and was compared with that of the commercial TiO₂ photocatalyst (Degussa P25). The results revealed that the nitrogen doping could lead to the response to visible light and that the ferrum doping could improve the photocatalytic performance. The effects of the component and the annealing temperature of the co-doped titania photocatalyst on the photocatalytic activity were investigated.     

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 and photochemical properties of HTaWO6/ (Pt,TiO2) nanocomposite under visible light irradiation

A new layered nanocomposite, HTaWO₆/(Pt, TiO₂) was synthesized using n-type semi-conductor HTaWO₆ as a host material. HTaWO₆ and HTaWO₆/TiO₂were white, while both HTaWO₆/Pt and HTaWO₆/(Pt, TiO₂) were yellow. The yellow color might be attributed to H_1-xTaWO_6-x/2 formed by the photo-induced phase transformation promoted by Pt. Although HTaWO₆/Pt showed absorption in visible light region (λ > 400 nm), the hydrogen evolution activity was negligibly small. On the other hand HTaWO₆/(Pt, TiO₂) showed excellent photocatalytic activities even under visible light irradiation. The sample containing rutile type titania such as TiO₂(P-25) also showed hydrogen evolution activity, but the activity was smaller than that of HTaWO₆/(Pt, TiO₂). These results suggested that rutile type titania, which can be excited by visible light of wavelength less than 413 nm, played an important role in the visible light-induced photocatalytic activity. The improvement of the hydrogen evolution activity of rutile type titania by intercalating into HTaWO₆/Pt may be due to the depression of the recombination of photoinduced electrons and holes by the heterogeneous electron transfer from rutile type TiO₂ to HTaWO₆/Pt.     

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.     

Efficient visible light-induced degradation of phenol on N-doped anatase TiO2 with large surface area and high crystallinity

The N-doped anatase TiO₂ photocatalysts were prepared via solvothermal and ethylenediamine reflux treatment, followed by the sequential calcination in air and NH₃/N₂ atmosphere. The resulting photocatalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and UV-vis diffuse reflectance spectra. The results revealed that the prepared N-doped anatase TiO₂ had characteristics of small crystallite size, large surface area, high crystallinity and visible light response. The prepared N-doped anatase TiO₂ photocatalysts showed much higher photocatalytic activity than N-doped Degussa P25 for the degradation of phenol under both ultraviolet and visible light irradiation, owing to more highly oxidizing hydroxyl radical which was the main oxidative species responsible for the degradation of phenol.     

硫和银共掺杂介孔TiO2的制备、表征及其对染料的光催化降解活性

以P123为模板,以钛酸四正丁酯、硝酸银和硫脲为原料采用模板法制备了一系列硫和银共掺杂介孔TiO₂光催化材料．利用SEM、XRD、BET和紫外-可见光谱等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征．以甲基橙溶液的光催化降解为模型反应,考察了不同掺杂量的样品在紫外和可见光下的光催化性能．结果表明,用模板法制备的共掺杂介孔TiO₂光催化材料在紫外和可见光条件下较纯介孔TiO₂和单掺杂介孔TiO₂对甲基橙溶液具有更好的光催化降解效果, 且硫和银的掺杂量及样品焙烧温度显著影响该材料的催化性能．当硫掺杂量为2mol%和银掺杂量为1mol%,在500 oC 焙烧2 h所得光催化材料的催化性能最佳,4 h即可使甲基橙的降解率达98.8%,重复使用4次仍可使甲基橙的降解率保持在87.5%以上     

Preparation of N-doped TiO<Subscript>2</Subscript> photocatalyst by atmospheric pressure plasma process for VOCs decomposition under UV and visible light sources

The nitrogen doped (N-doped) titanium dioxide (TiO₂) photocatalyst was prepared by the atmospheric-pressure plasma-enhanced nanoparticles synthesis (APPENS) process operated under normal temperature, i.e. the dielectric barrier discharge plasma process. The N₂ carrier gas is dissociated in the AC powered nonthermal plasma environment and subsequently doped into the TiO₂ photocatalyst that was capable of being induced by visible light sources. The APPENS process for producing N-doped TiO₂ showed a higher film deposition rate in the range of 60–94 nm/min while consuming less power (<100 W) as compared to other plasma processes reported in literatures. And the photocatalytic activity of the N-doped TiO₂ photocatalyst was higher than the commercial ST01 and P25 photocatalysts in terms of toluene removals in a continuous flow reactor. The XPS measurement data indicated that the active N doping states exhibited N 1s binding energies were centered at 400 and 402 eV instead of the TiN binding at 396 eV commonly observed in the literature. The light absorption in the visible light range for N-doped TiO₂ was also confirmed by a clear red shift of the UV-visible spectra.     

TiO2–carbon nanotube composites for visible photocatalysts – Influence of TiO2 crystal structure

We investigated the influence of the crystal structure of TiO₂ and the use of different TiO₂ precursors on the properties and photocatalytic activity of carbon nanotube (CNTs)–titania composites. We found that the crystal structure and properties of starting TiO₂ nanomaterial significantly affected the effect of CNTs incorporation on the photocatalytic activity under simulated solar and visible light illumination (simulated solar illumination with UV-blocking filter). In case of significant photocatalytic activity under visible light illumination (anatase TiO₂), likely due to the presence of native defects, composites exhibited lower activity under visible illumination only, but higher activity under simulated solar illumination. The opposite trends were observed for P25 (anatase + rutile) and rutile TiO₂, where incorporation of CNTs resulted in a significant increase of photocatalytic activity under visible illumination. Thus, control over crystal structure and native defects is essential for the development of efficient visible light activated photocatalysts.     

Photocatalytic photodegradation of xanthate over C, N, S-tridoped TiO2 nanotubes under visible light irradiation

C, N, S-tridoped TiO₂ nanotubes were synthesized via hydrothermal synthesis and post-treatment, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), the Brunauer-Emmett-Teller method (BET), and UV-vis diffuse reflectance spectroscopy (DRS). The UV-diffuse reflectance spectra of all the C, N, S-tridoped TiO₂ nanotubes greatly extended the absorption edge to the visible light region, and the absorbance in the visible region increased with increasing molar ratio of thiourea to Ti (R), which could be attributed to C, N, S-tridoping in the form of cation C-doping, interstitial N-doping, cation S-doping, and adsorbed ions’ states. The photocatalytic activity of C, N, S-tridoped TiO₂ nanotubes was evaluated by photocatalytic photodegradation of potassium ethyl xanthate (KEX) under visible light irradiation. It was found that the photocatalytic activity of the prepared samples increased with increasing molar ratio of thiourea to Ti (R). At R=6, the photocatalytic activity of the tridoped sample TNTS-6 reached a maximum value. With further increase in R, photocatalytic activity of the sample decreased, which could be attributed to the high visible light activity resulting from the balance between visible light absorption and recombination of electron/hole pairs.     

Low-temperature preparation of anatase titania-coated magnetite

A composite photocatalyst with an anatase titania shell and a magnetite core was prepared in a novel way at low temperature (75 °C at most) by coating photoactive titanium dioxide onto a magnetic Fe₃O₄ core. The photocatalytic activity of the prepared photocatalyst was evaluated by the degradation of model contaminated water of phenol and compared to single-phase titania (either Degussa P25 or prepared titania without magnetic Fe₃O₄). The results showed that the photoactivity was slightly depressed. Then, a remarkable improvement in photoactivity was achieved by modifying the photocatalyst with a SiO₂ layer between the Fe₃O₄ core and TiO₂ shell. The repetitive using of the modified photocatalyst was also investigated, and experimental results illustrated that the photocatalytic-degraded ratio of phenol was still higher than 80% after six cycles.     

Preparation, characterization and photocatalytic activity of polycrystalline Bi2O3/SrTiO3 composite powders

Bi₂O₃/SrTiO₃ composite powders have been prepared and their photocatalytic activities were investigated by photooxidation of methanol. These powders were characterized by UV-Visible diffuse reflectance spectra, SEM and X-ray diffraction (XRD). The results revealed that all the Bi₂O₃/SrTiO₃ composite powders exhibited higher photocatalytic activity than pure SrTiO₃, Bi₂O₃ and TiO₂ (P25) under visible light irradiation (λ>440 nm). The effects of the Bi₂O₃ contents on the photocatalytic activities of the composite powders were examined, the photocatalytic activities increased with the content of Bi₂O₃ increasing to a maximum of 83% and then decreased under visible light irradiation. The effects of the calcination temperatures on the photocatalytic activities of the composite powders were also investigated.     

Band structure and photocatalytic properties of perovskite-type compound Ca2NiWO6 for water splitting

An oxide semiconductor Ca₂NiWO₆, with double-perovskite crystal structure, was synthesized by solid-state reaction method. The compound Ca₂NiWO₆ was characterized by X-ray diffraction, UV-visible diffuse reflectance, and photoluminescence. The photocatalytic properties of the compound for water splitting were investigated under UV and visible light irradiation. The results showed H₂ evolution was not observed over the compound under visible light irradiation (λ>420 nm) with a 300 W xenon arc lamp when using methanol (CH₃OH) as electron donor, although the compound was responsive to visible light region. Based on the experimental results, a possible band structure was proposed through theoretical calculation of the electronic structure by using the full potential-linearized augmented plane wave (F-LAPW). The band structure and photocatalytic properties were attributed to the special crystal and electronic structures. Due to the oxygen vacancies in the compound, which worked as electron-hole recombination centers, the photocatalytic activity of the compound was low.     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

Photophysical and enhanced daylight photocatalytic properties of N-doped TiO2/g-C3N4 composites

N-doped TiO₂/C₃N₄ composite samples were synthesized by heating the mixture of the hydrolysis product of TiCl₄ and C₃N₄ at different weight ratios. The samples were characterized by X-ray diffraction (XRD), Raman spectrum, UV–vis absorption spectrum, photoluminescence spectrum, X-ray photon electron spectrum (XPS) and surface photovoltage spectrum (SPS). The XRD and Raman results indicate that the introduction of C₃N₄ could inhibit the formation of rutile TiO₂. The composite samples show slight visible light absorption due to the introduction of C₃N₄. The XPS result reveals that some amount of nitrogen is doped into TiO₂, and C₃N₄ exists in the composite sample. The intensities of the SPS signal in the composite samples decrease with the rise in the amount of C₃N₄ in the samples. The photocatalytic activity was evaluated from the Rhodamine B (RhB) degradation under fluorescence light irradiation. The composite samples show significantly enhanced photocatalytic activities and the RhB self-sensitized photodegradation in this system was observed by measuring the photocurrent in the dye sensitized solar cell using the composite as the working electrode.     

Effects of microwave drying on the microstructure and photocatalytic activity of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with highly photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate as precursor, and then dried in microwave oven. The prepared samples were characterized by XRD, SEM, TEM, HRTEM and N₂ adsorption-desorption measurement. The photocatalytic activity was evaluated by the photocatalytic degradation of acetone in air under UV light irradiation at room temperature. The effects of microwave drying on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. The results show that microwave drying not only promotes the growth of the pores but also greatly reduces the state of agglomeration within the powders. All the microwave-dried TiO₂ powders show higher photocatalytic activity than Degussa P-25 (P25) and the TiO₂ powders dried by conventional method.