Synthesis of crystal-phase and color tunable mixed anion co-doped titanium oxides and their controllable photocatalytic activity

B and N mixed anions co-doped titania with various crystal phases such as anatase,brookite,and rutile were successfully synthesized by a hydrothermal synthesis followed by heat treatment in an ammonia gas atmosphere at 550-650℃(denoted as BN-Ana_x,BN-Bro_x,and BN-Rut_x,x is the treatment temperature).The colors of as-prepared BN-Ana,BN-Bro,and BN-Rut are red,yellow-green,and cyangreen,respectively.The color changing mechanism of titania was related to their various band gap structure and the existence of B-N bonding.The nitridation temperature exhibits effective color changing compared to that of nitridation time.The different phases of the mixed anion codoped titania possess different photocatalytic deNO_(x) activity.The BN-Ana and BN-Rut show poor photocatalytic deNO_(x) activity,while the BN-Bro shows excellent photocatalytic deNO_(x) activity,better than that of standard titania photocatalyst Degussa P25.The colorful titania with low-photocatalytic activity is heavy metal elements free,indicating their possible applications as nontoxic color pigments or novel cosmetic raw materials.

Preparation of Nano-TiO_2 Doped with Cerium and Its Photocatalytic Activity

Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and UV/Vis diffuse reflectance spectra （DRS）. The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.

Synthesis of iron(Ⅲ)-doped nanostructure TiO_2/SiO_2 and their photocatalytic activity

Iron（Ⅲ）-doped nanostructure TiO2-coated SiO2 （TiO2/SiO2） particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing the sol-gel method with TiChas a precursor. The samples were characterized by Fourier transform infrared spectroscopy （FTIR）, SEM, EDS, XPS, and XRD. The experimental results show that TiO2 nanopowders on the surface of SiO2 particles are well distributed, the amount of TiO2 is increased with the adding of coating layers, the pure anatase-TiO2 coating layers are synthesized at 500℃, and the photocatalytic activity of Fe^3＋-doped TiO2/SiO2 is higher than that of undoped TiO2/SiO2.

Grain Size and Photocatalytic Activity of Nanometer TiO_2 Thin Films Prepared by the Sol-gel Method

Transparent anatase TiO2 nanometer thin films with photocatalytic activity were prepared via the sol-gel method on soda-lime glass. The thickness , crystalline phase, grain size, surface hydroxyl amount and so on were characterized by scanning electron microscopy (SEM) , X-ray diffraction (XRD), transmission electron microscopy ( TEM), X-ray photoelectron spectroscopy (XPS) and UV-visible spectrophotometer ( UV-VIS). The photocatalytic activity of TiO2 thin films was evaluated for the photocatalytic decolorization of aqueous methyl orange . The effects of film thickness on the crystalline phase, grain size, transmittance and photocatalytic activity of nanometer Ti02 thin films were discussed.

Rapid communication Preparation of TiO_2 nanometer thin films with high photocatalytic activity by reverse micellar method

Two kinds of TiO_2 nanometer thin films were prepared on stainless steel bythe reverse micellar and sol-gel methods, respectively. The calcined TiO_ 2 thin films werecharacterized by X-ray diffraction (XRD), atomic force microscopy (AFM), BET surface area and X-rayphotoelectron spectroscopy (XPS). Photocatalytic activity was evaluated by photocatalyticdecoloration of methyl orange aqueous solution. The results showed that the TiO_2 thin filmsprepared by reverse micellar method (designated as RM-TiO_2 films) showed higher photocatalyticactivity than those by sol-gel method (designated as SG-TiO_2 films). This is attributed to the factthat the former is composed of smaller monodispersed spherical particles with a size of about 15 nmand possesses higher surface areas.

Enhanced photocatalytic activity of (La, N) co-doped TiO_2 by TiCl_4 sol-gel autoigniting synthesis

（La, N） co-doped TiO2 photocatalysts were synthesized using TiC14 sol-gel autoignidng synthesis （SAS） starting from a complex compound system of TiCl4-La（NO3）3-citric acid-NH4NO3-NHyH2O, in which the （La, N） co-doped process was accompushed in the formation of TiO2 nanocrystals. The prepared samples were characterized by using X-ray diffraction （XRD）, X-ray photoemission spectroscopy （XPS） and UV-vis diffuse reflectance spectra. The results indicated that nitrogen and lanthanum were incorporated into the lattice and interstices of titania nanocrystals, which resulted in narrowing the band gap and promoting the separation of photoexcited hole-electron pairs, respectively, and showing expected red-shifts and enhanced photocatalytic activity under visible light. The mechanism on nitrogen doping and enhancement in photocatalyfic activity of （La, N） co-doped titania by SAS was discussed in detail.

Efect of light response on the photocatalytic activity of BiOClxBr1-x in the removal of Rhodamine B from water

BiOClxBr1-x catalysts were synthesized through an alcoholysis method and characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HRTEM）, and diffuse reflectance spectroscopy （DRS）. The as-prepared photocatalysts were found to be tetragonal crystal structure and lamellar plate morphology. Their band gaps were between 3.44 and 2.83 eV. The effect of light response on the photocatalytic activity of BiOClxBrl-x was investigated by degradation of Rhodamine B （RhB）. Complete removal of RhB from water was realized under simulated sunlight irradiation for 50 min with BiOC10.5Br0.5. Mechanism studies showed that photo- generated holes and superoxide anion radicals played important roles in RhB photodegradation. The results of chemical oxygen demand （COD） confirmed RhB mineralization. The effect of light response on the activity of BiOClxBr1-x was further investigated under monochromatic light irradiation, and BiOCl0.5Br0.5 catalyst exhibited the highest activity. Furthermore, BiOC10.5Br0.5 exhibited high stability, suggesting its practical application for the removal of RhB pollutant from water.

Effect of Preparation Methods of Bi_(2)O_(3) Nanoparticles on their Photocatalytic Activity

Bi 2O 3 nanoparticles were prepared by means of ammonia precipitation, polyol mediated methods and microemulsion chemical method. The structure and properties of the as-prepared nanoparticles, having been submitted to a heat-treatment test at 750 ℃, were characterized by means of XRD, BET, XPS and UV-Vis absorption techniques. The photocatalytic oxidation reactions of benzene, toluene and xylene were used as the model reaction to measure the photocatalytic activity of Bi 2O 3 nanoparticles, respectively. The results show that the crystallite size of Bi 2O 3 prepared with different methods and calcined at 750 ℃ were 50.6, 38.5 and 31.5 nm, respectively. The photocatalytic activity of Bi 2O 3 nanoparticles prepared with the microemulsion chemical method was higher than that of the particles prepared with the polyol mediated method; and that of the particles prepared with the micromulsion chemical method was the highest among the three. The degradation rates of the three pollutants xylene, toluene and benzene decreased in sequence.

Surface ζ potential and photocatalytic activity of rare earths doped TiO_2

The iso-electric point of different rare earths （La, Ce, Y） doped anatase TiO2 was set out, and three organisms with different sur- face electrical properties （methylene blue trihydrate-positive electricity, methyl orange-negative electricity, methyl red-neutral electricity） were selected as photodegradable models. The result showed that the photocatalytic activity of 0.5wt.%Y ions doped anatase TiO2 was better than those of the others. The relationship between Zeta （ξ） potential and the photocatalytic activity of different RE doped anatase TiO2 were also investigated. The Y-doped anatase TiO2 was found with the special two iso-electric points and three ξ potential values.

Photocatalytic Activity of TiO_(2) Coatings Fabricated on Al_(2)O_(3) by Mechanical Coating Technique

The titanium coatings were prepared on Al_(2)O_(3) balls by mechanical coating technique (MCT),and then the coatings were oxidized to titanium oxides(TiO_(2)) films at 300-600 ℃.The effects of different milling time and oxidation temperature on thickness of films were studied.The composition and microstructure of the films were analyzed by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS).The results show that the thickest coatings with an average thickness of 20 μm were obtained at the milling time of 15 h.In addition,with the increase of the oxidation temperature,the oxidation of the film is increased.When the milling time is 15 h,the oxidation temperature is 500 ℃,and the addition of photocatalyst is 1 g/mL.The films have the best photocatalytic performance when the degradation rate of methyl orange solution reaches the maximum value of 74.9 %,and the films have a good reusability.

Fe_2O_3-Modified Porous BiVO_4 Nanoplates with Enhanced Photocatalytic Activity

As BiVO4 is one of the most popular visible-light-responding photocatalysts, it has been widely used for visiblelight-driven water splitting and environmental purification. However, the typical photocatalytic activity of unmodified BiVO4 for the degradation of organic pollutants is still not impressive. To address this limitation, we studied Fe2O3-modified porous BiVO4 nanoplates. Compared with unmodified BiVO4, the Fe2O3-modified porous Bi VO4 nanoplates showed significantly enhanced photocatalytic activities in decomposing both dye and colorless pollutant models, such as rhodamine B(Rh B) and phenol,respectively. The pseudo-first-order reaction rate constants for the degradation of RhB and phenol on Fe2O3-modified BiVO4 porous nanoplates are 27 and 31 times larger than that of pristine Bi VO4, respectively. We also found that the Fe2O3 may act as an efficient non-precious metal co-catalyst, which is responsible for the excellent photocatalytic activity of Fe2O3/BiVO4.Graphical Abstract Fe2O3, as a cheap and efficient co-catalyst, could greatly enhance the photocatalytic activity of Bi VO4 porous nanoplates in decomposing organic pollutants.

In-Situ Hydrothermal Synthesis of Bi–Bi2O2CO3 Heterojunction Photocatalyst with Enhanced Visible Light Photocatalytic Activity

Bismuth containing nanomaterials recently received increasing attention with respect to environmental applications because of their low cost, high stability and nontoxicity. In this work, Bi–Bi_2O_2CO_3 heterojunctions were fabricated by in-situ decoration of Bi nanoparticles on Bi_2O_2CO_3 nanosheets via a simple hydrothermal synthesis approach. X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and high-resolution TEM(HRTEM) were used to confirm the morphology of the nanosheet-like heterostructure of the Bi–Bi_2O_2CO_3 composite. Detailed ultrafast electronic spectroscopy reveals that the in-situ decoration of Bi nanoparticles on Bi_2O_2CO_3 nanosheets exhibit a dramatically enhanced electron-hole pair separation rate, which results in an extraordinarily high photocatalytic activity for the degradation of a model organic dye, methylene blue(MB) under visible light illumination. Cycling experiments revealed a good photochemical stability of the Bi–Bi_2O_2CO_3 heterojunction under repeated irradiation. Photocurrent measurements further indicated that the heterojunction incredibly enhanced the charge generation and suppressed the charge recombination of photogenerated electron-hole pairs.

Preparation and photocatalytic activity of Cu^(2+)-doped TiO_2/SiO_2

Cu^2＋-doped nanostructured TiO2-coated SiO2 （TiO2/SiO2） particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized by the sol-gel method using TiOSO4 as a precursor. The experimental results showed that TiO2 nanopowders on the surface of SiO2 particles were well distributed and compact. The amount of TiO2 increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550℃. The 2-layer coated TiO2 particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu^2＋-doped TiO2/SiO2 was higher than that ofundoped TiO2/SiO2. The optimum dopant content was about 0.10wt%.

Effect of Tb_2O_3 additive on structure of anatase and photocatalytic activity of TiO_2/(O'+β')-Sialon multi-phase ceramics

Effect of rare earth oxide Tb2O3 additive on transformation behavior and grain growth of anatase and photocatalytic activity for TiO2/（O′＋β′）-Sialon multi-phase ceramic was investigated and the mechanism was discussed. X-ray diffractometer （XRD） was employed for the analysis of phase composition, grain size and lattice parameters of anatase. Photocatalytic activity of the composites was investigated through its photocatalytic degradation to methylene blue （MB） solution. The results showed that Tb2O3 significantly inhibited the transformarion process, which displayed an appreciably intensified effect with increasing Tb2O3 content. It could be attributed to the coaction of the active and passive influence mechanisms. For Tb3＋ entering TiO2 lattice, replacing Ti4＋ accelerated the transformation, whereas the lattice distortion caused by it was unfavorable for the process. On the other hand, the redox reaction between Tb3＋ and TiO2 as well as the Tb2O3 deposited on the surface of TiO2 inhibited the transformation. The addition of Tb2O3 effectively restrained the grain growth of TiO2 and the effect became significant with the increase of its content. With the increase of Tb2O3 addition, the photocatalytic activity of the catalysts increased and then dropped after reaching the maximum at about 2%. The action mechanism of Tb2O3 could be attributed to its optical properties and its effect on phase transformation, grain growth and crystal structure of TiO2.

Synthesis of TiO_2 films on glass slides by the sol-gel method and their photocatalytic activity

Titanium dioxide （TiO2） films with rod-like and sphere-like TiO2 particles were prepared on glass slides employing the sol-gel method. The shape and size of TiO2 particles were controlled using different concentrations of sodium dodecylbenzensulfonate （SDBS）. By increasing the mole ratio of SDBS, the shape of TiO2 particles transformed from rod-like to sphere-like. Also, the size of TiO2 particles became gradually smaller. Then, the size became bigger when an excess amount of SDBS was added. The films were mainly composed of anatase titania and the relative content of anatase increased with the increasing amount of SDBS. The photocatalytic activity of the TiO2 films that were added with SDBS was higher than that without SDBS. When the concentration of SDBS was 8.0 at%, the sample exhibited the best photocatalytic activity.

Effects of Nitrogen Doping on Microstructure and Photocatalytic Activity of Nanocrystalline TiO_2 Powders

Nitrogen-doped TiO2 nanocrystalline powders were prepared by hydrolysis of tetrachloride titanium （TiCl4） in a mixed solution of ethanol and ammonium nitrate （NH4NO3） at ambient temperature and atmosphere followed by calcination at 400 ℃ for 2 h in air. FTIR spectra demonstrate that amine group in original gel is eliminated by calcination, and the TiO2 powder is liable to absorb water onto its surface and into its capillary pore. XRD and SEM results show that the average size of nanocrystalline TiO2 particles is no more than 60 nm and with increasing the calcination temperature, the size of particles increases. XPS studies indicate the nitrogen atom enters into the TiO2 lattice and occupies the position of oxygen atom. The nitrogen doping not only depresses the grain growth of TiO2 particles, but also reduces the phase transformation temperature of anatase to futile. The photocatalytic activity of the nitrogen-doped TiO2 powders has been evaluated by experiments of photocatalytic degradation aqueous methylene blue.

Preparation and Photocatalytic Activity of Nanocrystalline GdFeO_3

With Gd2O3, Fe （NO3）3· 9H2O, and nitric acid （ 1： 1 volume fraction） as starting materials, nanocrystalline material of rare-earth composite oxide GdFeO3 with perovskite-type structure was synthesized by sol-gel method in the system of citric acid. Structural characteristics were characterized by XRD and TEM, which indicate that the sample is nanocrystallite with uniform grain size distribution and the average grain size is about 21 nm. Its crystal structure includes a certain amount of lattice distortion due to decrease of grain size and increase of surface area. Photocatalytic properties of this material were tested by decolorization of various water-soluble dyes. Effects of irradiation time and amount of GdFeO3 on photocatalytic activity were also investigated. The results show that nano-sized GdFeO3 exhibits high photocatalytic activity and that increase of irradiation time and the amount of GdFeO3 can improve its photocatalytic activity.

Enhanced photocatalytic activity of nanotube-like titania by sulfuric acid treatment

The TiO 2 nanotube sample was prepared via a NaOH solution in a Teflon vessel at 150℃. The as-prepared nanotubes were then treated with H 2SO 4 solutions. The TiO 2 nanotube has a crystalline structure with open-ended and multiwall morphologies. The TiO 2 nanotubes before and after surface acid treatment were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and UV-VIS dispersive energy spectrophotometry(DRS). The photocatalytic activity of the samples was evaluated by photocatalytic degradation of acid orange II in aqueous solutions. It was found that the order of photocatalytic activity was as follows: TiO 2 nanotubes treated with 1.0 mol/L H 2SO 4 solution (TiO 2(1.0M H 2SO 4) nanotubes)>TiO 2 nanotubes treated with 0.2 mol/L H 2SO 4 solution (TiO 2(0.2M H 2SO 4) nanotubes)>TiO 2 nanotubes >TiO 2 powder. This was attributed to the fact that TiO 2 nanotubes treated with H 2SO 4 was composed of smaller particles and had higher specific surface areas. Furthermore, the smaller TiO 2 particles were beneficial to the transfer and separation of photo-generated electrons and holes in the inner of and on the surface of TiO 2 particles and reduced the recombination of photo-generated electrons and holes. Acid treatment was particularly effective for TiO 2 nanotubes, this increase in activity was correlated with the concentration of H 2SO 4 solution.

Synthesis and Photocatalytic Activity of Fe-doped TiO_2 Supported on Hollow Glass Microbeads

In this paper, Fe-doped TiO_2 photocatalyst supported on hollow glass microbeads(Fe-TiO_2 /beads)is prepared by dip-coating method, which uses hollow glass microbeads as the carriers and tetrabutylorthotitanate [Ti(OC_4H_9)_4] as the raw material. The phase structure, ingredient, morphologies, particle size and shell thickness of the products are characterized by X-ray powder diffraction(XRD), energy-dispersive spectroscopy(EDS) and field emission scanning electron microscope(FESEM). The feasibility of photocatylic degradation of Rhodamine B(Rh B) under illumination of UV-vis light is studied. The results show that the core-shell structure catalyst is composed of Fe-doped anatase TiO_2 and hollow glass microbeads, and the catalytic activity of the TiO_2 is markedly enhanced by Fe ion doping. The optimum concentration of Fe ion is 0.1%(molecular fraction) in the precursor and the photocatalytic activity can be increased to 98% compared with that of the undoped one. The presence of ferrum elements neither influences the transformation of anatase to rutile, nor creates new crystal phases. The possible mechanism of photocatalytic oxidation is also discussed.

Supercritical CO_(2)-Tailored 2D Oxygen-doped Amorphous Carbon Nitride for Enhanced Photocatalytic Activity

Simultaneously adjusting the surface,crystallographic and electronic structures of nanomaterials provide a new avenue for rational design of advanced photocatalyst yet it is challenging.In this work,a surface and structural engineering strategy is developed to simultaneously realize the 2D amorphous structure and oxygen(O)-doping in graphitic carbon nitride(g–C_(3)N_(4))via the assistance of supercritical carbon dioxide(SCCO_(2)).The 2D O-doped amorphous g-C_(3)N_(4)nanosheets display greatly enhanced photocatalytic CO_(2)reduction and methylene blue degradation performances.The synthesis method as well as the mechanism of the enhanced photocatalytic activity was investigated,wherein the introduction of 2D amorphous structure and O dopant in the g-C_(3)N_(4)contributes to the increased surface area,abundant active sites,wider visible-light absorption range and efficient charge separation property,and thus the outstanding photocatalytic activities can be obtained.Its photocatalytic CH_(4)evolution rate and MB degradation rete are 5.1 and 7.0 times enhancement over bulk crystalline g-C_(3)N_(4),respectively.This work presents a great promising way for designing and developing advanced photocatalysts.