Reconstruction and recovery of anatase TiO_(2) from spent selective catalytic reduction catalyst by Na OH hydrothermal method

The improper disposal of spent selective catalytic reduction (SCR) catalysts causes environmental pollution and metal resource waste.A novel process to recover anatase titanium dioxide (TiO_(2)) from spent SCR catalysts was proposed.The process included alkali (NaOH) hydrothermal treatment,sulfuric acid washing,and calcination.Anatase TiO_(2) in spent SCR catalyst was reconstructed by forming Na_(2)Ti_(2)O_(4)(OH)_(2) nanosheet during NaOH hydrothermal treatment and H_(2)Ti_(2)O_(4)(OH)_(2) during sulfuric acid washing.Anatase TiO_(2) was recovered by decomposing H_(2)Ti_(2)O_(4)(OH)_(2) during calcination.The surface pore properties of the recovered anatase TiO_(2) were adequately improved,and its specific surface area (SSA) and pore volume (PV) were 85 m^(2)·g^(-1)and 0.40 cm^(3)·g^(-1),respectively.The elements affecting catalytic abilities(arsenic and sodium) were also removed.The SCR catalyst was resynthesized using the recovered TiO_(2) as raw material,and its catalytic performance in NO selective reduction was comparable with that of commercial SCR catalyst.This study realized the sustainable recycling of anatase TiO_(2) from spent SCR catalyst.

Sonocatalytic degradation of methyl orange in the presence of (nanometer and ordinary) anatase TiO_2 powders

The nanometer and ordinary anatase titanium dioxide(TiO_2) powders were adopted as the sonocatalysts for the degradation of methyl orange used as a model compound for the first time. It was found that the sonocatalytic degradation effect of methyl orange in the presence of TiO_2 powder were much better than that without TiO_2, but the sonocatalytic activity of the nanometer anatase TiO_2 particle was obviously higher than that of ordinary anatase TiO_2 particle. Although there are many factors influencing sonocatalytic degradation of methyl orange, the experimental results showed that the best degradation ratio of methyl orange could be obtained when the experimental conditions were: initial concentration 15 mg/L, nanometer anatase TiO_2 adding amount 750 mg/L, ultrasonic frequency 40 kHz, output power 50 W, pH = 3.0 and temperature 40℃ within 150 min. In addition, the catalytic activity of reused nanometer anatase TiO_2 catalyst was also studied and found to decline gradually comparing with initial nanometer anatase TiO_2 catalyst. All experiments indicated that the method of the sonocatalytic degradation of organic pollutants in the presence of TiO_2 powder was an advisable choice for non- or low-transparent organic wastewaters.

Geology and Geochemistry of the Yangtizishan-Moshishan Metamorphosed Sedimentary Anatase Deposit in Zhenglan Qi,Inner Mongolia:Discovery of a New Genetic Type of Titanium Deposit

Anatase and its allomorphic mineral rutile have the most prominent economic significance among titanium mineral resources and constitute one of the badly needed mineral resources currently in China. The Yantizishan-Moshishan anatase deposit was formerly referred to as an iron deposit. Based on recent investigation and exploration the authors believe that it is actually a large metamorphosed sedimentary anatase-dominated deposit belonging to a new genetic type. Ore bodies occur in stratoid and lenticular forms in Mesoproterozoic （1751 Ma） schist, metasandstone （metasiltstone）, and amphibolite. Rich ores have perthitic structure comprising chiefly interbedded quartz perthite （with disseminated anatase and rutile） and anatase perthite. Ore minerals are mainly anatase and subordinately rutile and ilmenite （±hematite）, while nonmetallic minerals are chiefly quartz with a certain amount of anthophyllite and biotite （±garnet）. The grain sizes of anatase, ruffle and ilmenite are 0.01-0.1 mm. Rich ores contain 3.14% to 15.46% TiO2. averaging 6.91%, while the low-grade ores have TiO2 content about 1.2%to 2.97%, averaging 1.76%. The ores have relatively high TFe and V contents. Trace elements in anatase and rutile such as Nb and Cr were analyzed by the electron microprobe. According to their relatively low Nb and Cr contents, source anatase and rutile must have come from meta-mafic rocks. Trace elements of the associated ilmenite show relatively high MnO and low MgO contents, just in contrast to those of ilmenite in V-Ti-magnetite ores of magmatic origin. The protoliths of amphibolite wall rocks should be basalt and picrite-basalt. Pertochemical data suggest that the tectonic setting of these rocks belongs to an island arc or a transitional belt between the island arc and oceanic ridge. Silicon isotope study shows that δ30Si values of different anatase ores, quartzite, and schist in this deposit are 0.1‰ to -0.9‰, similar to those of marine hydrothermal exhalative sedimentary deposits. All of these geological and geochemical characteristics of the ore deposit suggest that the anatase ores and amphibolite are products of submarine basic volcanism. The ores had chemical precipitation features, but were later subjected to regional intermediate （or somewhat lower） grade metamorphism （1158 Ma）. Rutile was formed mainly in the process of this metamorphism. The ore belt locally underwent hydrothermal modification during the emplacement of Late Yanshanian granite （118 Ma）.

Mixed Phase Anatase/rutile Titanium Dioxide Nanotubes for Enhanced Photocatalytic Degradation of Methylene-blue

Titanium dioxide Nanotubes(TNTs) prepared by electroless deposition have been annealed at air ambient and low temperature. As a result, the anatase/rutile phase composition of the TNTs can be tailored to the needs of later applications. Nanotubes with anatase/rutile mixed phase ratio of 4:1 have been produced in this report and further examined for their photocatalytical behavior. The photocatalytical properties of the TNTs have been observed by degradation of methylene-blue in aqueous solution under low power UV-light irradiation. The results shown in this report are based on the synergetic effect between rutile and anatase,which results in the mixed phase TiO 2 nanotubes having enhanced photocatalytical properties.

Preparation and Photocatalytic Behaviors of Nanoporous Polyoxotungstate-Anatase TiO_2 Composites

Nanoporous anatase TiO2 crystalline particles coupled with Keggin or Wells-Dawson unit, H3PW12O40/TiO2 or H6P2W18O62/TiO2, were prepared at a low temperature （200℃ ） using sol-gel method combined with hydrothermal treatment at programmed temperature. The as-prepared composites have uniform anatase phase, and they exhibit both micrand mesoporosities with pore sizes of 0.6 and 4.0 nm, respectively, and their average size is lower than 10 nm. Photocatalytic tests show the composites exhibit relatively higher photocatalytic activities to decompose the organocholorine pesticide hexachlorobenzene（HCB） than anatase TiO2, the starting polyoxotungstates, and EuEOa/TiO2 prepared by using sol-gel method, and this was attributed to （ 1 ） the synergistic effect of photoactive anatase TiO2 with the polyoxotungstate, and （2） the fascinating physical and chemical properties of the porous materials.

Low-temperature Preparation of Photocatalytic TiO_2 Thin Films on Polymer Substrates by Direct Deposition from Anatase Sol

Anatase TiO2 sol was synthesized under mild conditions （75℃ and ambient pressure） by hydrolysis of titaniumn-butoxide in abundant acidic aqueous solution and subsequent reflux to enhance crystallization. At room temperature and in ambient atmosphere, crystalline TiO2 thin films were deposited on polymethylmethacrylate （PMMA）, SiO2-coated PMMA and SiO2-coated silicone rubber substrates from the as-prepared TiO2 sol by a dip-coating process. SiO2 layers prior to TiO2 thin films on polymer substrates could not only protect the substrates from the photocatalytic decomposition of the TiO2 thin films but also enhance the adhesion of the TiO2 thin films to the substrates. Field-emission type scanning electron microscope （FE-SEM） investigations revealed that the average particle sizes of the nanoparticles composing the TiO2 thin films were about 35-47 nm. The TiO2 thin films exhibited high photocatalytic activities in the degradation of reactive brilliant red dye X-3B in aqueous solution under aerated conditions. The preparation process of photocatalytic TiO2 thin films on the polymer substrates was quite simple and a low temperature route.

Reversible Al^(3+) storage mechanism in anatase TiO_(2) cathode material for ionic liquid electrolyte-based aluminum-ion batteries

Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevertheless, to date, one of the major barriers to pursuit better AIB is the limited applicable cathode materials with the ability to store aluminum highly reversibly. Herein, a highly reversible AIB is proposed using mesoporous TiO2 microparticles(M-TiO2) as the cathode material. The improved performance of Ti O2/Al battery is ascribed to the high ionic conductivity and material stability, which is caused by the stable architecture with a mesoporous microstructure and no random aggregation of secondary particles. In addition, we conducted detailed characterization to gain deeper understanding of the Al^(3+) storage mechanism in anatase Ti O2 for AIB. Our findings demonstrate clearly that Al^(3+)can be reversibly stored in anatase TiO2 by intercalation reactions based on ionic liquid electrolyte. Especially, DFT calculations were used to investigate the accurate insertion sites of aluminum ions in M-Ti O2 and the volume changes of M-TiO2 cells during discharging. As for the controversial side reactions in AIBs, in this work, by normalized calculation, we confirm that M-Ti O2 alone participate in the redox reaction. Moreover, cyclic voltammetry(CV) test was performed to investigate the pseudocapacitive behavior.

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.

Photocatalytic and Photoelectronic Properties of Anatase TiO_2 Modified by Cu Ions Plasma and Its Theoretic Study by the First Principle Study

Highly oxidation. SEM analysis ordered anatase titania nanotube method was used to characterize arrays （TINT） were fabricated by anodic the morphology of the prepared samples. TiNT samples doped with Cu ions were prepared by home-made Metal Vapor Vacuum Arc ions sources （MEVVA, BNU, China） implanter. Photo-electric response and methyl orange decomposition ability of implanted samples under UV and visible light were tested, and the results indicated that the performance of Cu/TiNT enhanced significantly under visible light; it was noteworthy that the photocurrent density of A-Cu/TiNT was 0.102 mA/cm^2, which was 115 times that of pure TINT, and degradation ability of TiNT also strongly enhanced under visible light. In a word, the absorption spectrum of implanted anatase titania shifted to a longer wavelength region. Theoretic study on Cu-doped anatase based on density functional theory was carried out in this paper to validate the experiment results. The calculation results are depicted as follows： Intermittent energy band appeared around the Fermi energy after doping with Cu metal, the width of which was 0.35 eV and the location of valence and conduction bands shifted to the lower energy level by 0.22 eV; more excitation and jump routes were opened for the electrons. The narrowed band gaps allowed the photons with lower energy （at longer wavelength, such as visible light） to be absorbed, which accorded well with the experimental results.

Calculation of Electronic Structure of Anatase TiO_2 Doped with Transition Metal V,Cr,Fe and Cu Atoms by the Linearized Augmented Plane Wave Method

The electronic density of states and band structures of doped and un-doped anatase TiO2 were studied by the Linearized Augmented Plane Wave method based on the density functional theory. The calculation shows that the band structures of TiO2 crystals doped with transition metal atoms become narrower. Interesting, an excursion towards high energy level with increasing atomic number in the same element period could be observed after doping with transition metal atoms.

Photocatalytic Degradation of Rhodamine B Dye with High Purity Anatase Nano-TiO_2 Synthesized by a Hydrothermal Method

High purity anatase nano-TiO2 powders with high photocatalytic activity were prepared by a hydrothermal synthesis method. X-ray diffraction （XRD）, field emission transmission electron microscopy （FETEM）, ultraviolet-visible （UV-Vis） light absorption spectrum and photoluminescence （PL） spectrum were adopted to characterize the catalyst. Effects of temperature, time and sol concentration of hydrothermal synthesis on particle size and phases were investigated. Photocatalytic activities in the degradation of Rhodamine B Dye were studied. The experimental results indicated that photocatalytic activity of the nano-TiO2 powers was much higher than that of P25 （Degussa）.

Interaction of Photoactive[Fe(CN)_6]^(4-) with TiO_2 Anatase(101) Surface:A Periodic Density Functional Theory Study

The plane-wave pseudopotential function method, based on density-functional theory, has been used to calculate the adsorption, electronic band structures, orbitals and optical absorption spectrum of [Fe（CN）6]^4- on TiOz anatase（101） surface. Our calculations reveal that the surface-modified anatase system has large adsorption energy and a much narrower band gap. [Fe（CN）6]^4- adsorption on the （101） surface could lead to a large red shift of the anatase optical absorption threshold, which extends into a visible region significantly. The calculated results are in agreement with the experiment and other theoretical studies reasonably. It is very important for the understanding and further development ofphotovoltaic materials that are active under visible light.

First-principle Calculations of V/Fe Doped Anatase TiO_2

The electronic structures of the titanium dioxide（TiO2） doped with V and Fe were analyzed by using first-principle calculations based on the density functional theory（DFT） with the full potential linearized augmented plane wave method （FP-LAPW）. The fully optimized structure and the relaxation introduced by impurity were obtained by minimizing the total energy and atomic forces. The unit cell of the V-doped anatase TiO2 is smaller than that of the non-doped one, but for the Fe-doped one, the case is just the opposite. It is found that the apical Ti-O and impurity-O bond lengths of the V/Fe-doped anatase TiO2 are greater than those of the non-doped structure, but smaller for the equatorial bond length. Through the band structures and the density of states, the V-doped TiO2 is shown to be a kind of half-metal, while the Fe-doped TiO2 a kind of metal. The magnetic moments of the V/Fe-doped system are mainly generated by the dopants. The results may be helpful for us to understand the experimental outcome of this system.

A simple and novel synthetic route to prepare anatase TiO2 nanopowders from natural ilmenite via the H3PO4/NH3 process

A simple and novel technique for the preparation of anatase TiO2 nanopowders using natural ilmenite(FeTiO3)as the starting material is reported.Digesting ilmenite with concentrated H3PO4 under refluxing conditions yields a whiteα-titanium bismonohydrogen orthophosphate monohydrate(TOP),Ti(HPO4)2·H2O,which can be easily isolated via gravity separation from unreacted ilmenite.The addition of ammonia to the separated TOP followed by calcination at 500°C completes the preparation of anatase TiO2.Calcination at temperatures above 800°C converts the anatase form of TiO2 to the stable rutile phase.The removal of iron from ilmenite during the commercial production of synthetic TiO2 is problematic and environmentally unfriendly.In the present study,the removal of iron was found to be markedly simple due to the high solubility of iron phosphate species in concentrated H3PO4 with the precipitation of TOP.The titanium content of the prepared samples on metal basis with silica and phosphorous as major impurities was over 90%.Prepared TiO2 samples were characterized using X-ray fluorescence,Fourier-transform infrared spectroscopy,Raman spectroscopy,ultraviolet–visible diffuse reflectance spectroscopy,high-resolution transmission electron microscopy,and X-ray diffraction analyses.The photocatalytic potentials of the commercial and as-prepared TiO2 samples were assessed by the photodegradation of rhodamine B dye.

Crystallization Behavior of Anatase Films in Applied Electric Field Heating Process

In this research the TiO2 thin films were prepared by sol-gel dip coating. The crystallization of the films in the applied electric field heating process was thoroughly studied by many technique, differential thermal analysis (DTA), Raman spectroscopy and atomic force microscope (AFM). Furthermore the phase formation, microstructure and photo-catalytic activity of TiO2 film were studied under the condition of an electric field heating-treatment. It is found that the existence of applied electric field promotes the phase transformation from anatase to rutile. Studies on photo-catalytic degradation show that the photo-catalytic activity of TiO2 thin films in an applied electric field is higher.

The adsorption and activation of formic acid on different anatase TiO2 surfaces

Formic acid photodegradation is one of the most important reactions in organic pollution control, and helps to improve the hydrogen generation efficiency in titanium dioxide catalyzed water photodecomposition. Based on density functional theory and Reax FF molecular dynamics, the adsorption, diffusion and activation of formic acid on the different anatase TiO（101）,（001）,（010） surfaces are investigated.The result shows that the adsorption of COOH on anatase TiOsurface shrinks the energy gap between the dehydrogenation intermediate COOH and HCOO. On the anatase TiO（101） surface, the formic acid breaks the O–H bond at the first step with activation energy 0.24 eV, and the consequent break of α-H become much easier with activation energy 0.77 eV. The dissociation of α-H is the determination step of the HCOOH decomposition.

Fabrication of anatase titanium dioxide nanotubes by electroless deposition using polycarbonate for separate casting method

Titanium dioxide nanotubes(TNTs)were prepared by electroless deposition using ion track etched polycarbonate templates.The ion tracks were prepared to the desired diameter of the TNTs outer diameter.Titanium dioxide nanotubes with a diameter of minimum 80 nm having a wall thickness of minimum 10 nm can be fabricated using this method.To achieve nanotubes with thin walls and small surface roughness the tubes were generated by a several steps procedure under aqueous conditions at nearly room temperature.The presented approach will process open end nanotubes with well defined outer diameter and wall thickness.Using this method TNT arrays up to 109 tubes per cm2having a tube length up to 30μm can be produced,single tubes are also possible.The structural properties of the grown TNTs were investigated by using various analytical techniques,i.e.scanning electron microscopy(SEM),energy dispersive X-ray fluoresence spectrometer(EDX),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),Raman spectroscopy and Photoluminescence.

Fe^(3+)-Doped Anatase TiO_2 Study Prepared by New Sol-Gel Precursors

FeTi_1-O_2（= 0.00,0.05,0.10） nanocomposites are synthesized using a sol-gel method involving an ethanol solvent in the presence of ethylene glycol as the stabilizer,and acetic acid as the chemical reagent.Their structural and optical analyses are studied to reveal their physicochemical properties.Using the x-ray diffractometer（XRD）analysis,the size of the nanoparticles（NPs） is found to be 18-32 nm,where the size of the NPs decreases down to 18 nm when Fe impurity of up to 10% is added,whereas their structure remains unchanged.The results also indicate that the structure of the NPs is tetragonal in the anatase phase.The Fourier transform infrared spectroscopy analysis suggests the presence of a vibration bond（Ti-O） in the sample.The photoluminescence analysis indicates that the diffusion of Fe^（3＋） ions into the TiO_2 matrix results in a decreasing electron-hole recombination,and increases the photocatalytic properties,where the best efficiency appears at an impurity of10%.The UV-diffuse reflection spectroscopy analysis indicates that with the elevation of iron impurity,the band gap value decreases from 3.47 eV for the pure sample to 2.95 eV for the 10 mol% Fe-doped TiO_2 NPs.

A Fundamental DFT Study of Anatase(TiO2) Doped with 3d Transition Metals for High Photocatalytic Activities

Anatase（TiO_2） has been widely used in photocatalysis. However, it can only absorb near-ultraviolet light with a wavelength below approximately 388 nm due to a wide band gap. Therefore a modification should be made for anatase to increase its capability in utilizing more abundant visible light. We investigated the doped anatase with the most promising 3d transition metal elements, and the results showed that the visible light absorption intensity was increased significantly due to the reduced band gap and the cavitation effects. As compared to other 3d transition metals, Cu was found to be the most effective one in improving anatase photocatalytic effects. In addition, greater Cu concentration doped in the anatase increased the photocatalysis effects but reduced the anatase stability, therefore, an optimized Cu concentration should be considered to optimize the anatase photocatalysis activity.

Ultrasonic Degradation of Methyl Orange in Presence of Y2O3 Doping Anatase TiO2 Catalyst

Various affecting factors and degradation mechanism were studied on ultrasonic degradation of methyl orange adopting Y2O3 doping anatase TiO2 catalyst prepared in laboratory.In the experiment, the UV-VIS spectrophotometer was used to follow and inspect the degradation process of methyl orange.The results indicate that the ultrasonic degradation ratios of methyl orange in the presence of anatase TiO2 catalyst are much better than those without catalyst.Moreover, the catalytic performance of Y2O3 doping anatase TiO2 catalyst is obviously higher than that of anatase TiO2 catalyst without doping.The optimal conditions were adopted in this work and the degradation and COD elimination ratio of methyl orange got to98% and 99.0% in 90 min, respectively.