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.

Influence of cerium ions on the anatase-rutile phase transition of TiO_2 prepared by sol-gel auto-igniting synthesis

The anatase-rutile phase transformation of TiO_2 doped cerium up to 5 molpercent was studied by X-ray diffraction and X-ray photoelectron spectroscopy. The samples wereprepared by sol-gel auto-igniting synthesis process from a TiO(NO_3)_2-Ce(NO_3)_2-NH_4NO_3-citricacid complex compound system. The combusted amorphous powders were calcined at differenttemperatures. Significant structural changes were observed during the various stages of the phasetransformation. It was concluded that at low dopant contents, cerium ions were incorporated into theTiO_2 structure, and the anatase phase was stabilized; but at larger amounts, part of the dopantwas segregated on the surface of TiO_2 and the rutile formation was accelerated at elevatedcalcination temperature.

Unique Pulsed-Laser Deposition Production of Anatase and Rutile TiO₂on Al₂O₃

Two pure hexagonal phases of titanium dioxide, anatase and rutile, were grown on c-cut Al2O3 substrates via pulsed-laser deposition by changing only the growth and annealing conditions, but without changing the substrate, target, or working gas. Purity of each phase was confirmed by x-ray diffraction, the quality of each film was studied using atomic force microscopy and scanning electron microscopy, and the interface between each substrate and film was studied using x-ray photoelectron spectroscopy. A binding layer of Ti2O3 was found to explain anatase growth under the very large lattice mismatch conditions.

Rutile to Titanite Transformation in Eclogites and its Geochemical Consequences:An Example from the Sumdo Eclogite,Tibet

The formation of titanite coronae after rutile is common in retrograde high-to ultrahigh-pressure meta-mafic rocks,which provides a good opportunity to address the geochemical behavior of HFSE in crustal environments.In the Sumdo eclogite,titanite occurs either as a corona around rutile grains or as semi-continuous veins cross-cutting the major foliation,whereas rutile grains occur either as inclusions in garnet or omphacite or as a relict core surrounded by titanite.Textural relationships and trace elements characteristics of rutile and titanite with different occurrences indicate that both minerals preferentially incorporate Nb and Hf over Ta and Zr in aqueous fluid.Moreover,the breakdown of omphacite and epidote could release substantial amounts of aqueous fluids enriched in Ca,Si,Fe and REE,which would react with rutile to form titanite coronae and veins.During this process,water-insoluble elements,like HFSE and HREE,behave like mobile elements,but they do not migrate substantially out of the system,instead,tending to react in situ.This suggests that the aqueous fluids released during the retrograde metamorphic reactions in mafic rocks could not substantially transfer fluidimmobile elements into the overlying mantle wedge in subduction environments.

The discovery of TiO_(2)-Ⅱ,the α-PbO_(2)-structured high-pressure polymorph of rutile,in the Suizhou L6 chondrite

We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact structures,and tektite.Our microscopic,Raman spectroscopic,electron microprobe and transmission electron microscopic investigations have revealed:(1) All observed TiO_(2)-Ⅱ grains are related with ilmenite and pyrophanite;(2) TiO_(2)-Ⅱ occurs as needle-and leaf-shaped inclusions in llmenite and patch-,tape-shaped body in pyrophanite;(3)The composition of TiO_(2)-Ⅱ is identical with that of its precursor rutile;(4) The Raman spectrum of TiO_(2)-Ⅱ is in good agreement with that of natural and synthesized α-PbO_(2)-type TiO_(2);(5) TiO_(2)-Ⅱ occurs mainly in the form of well-ordered nano-domains and small mis-orientation among the domains can be observed.(6) All electron diffraction reflections from TiO_(2)-Ⅱ can be indexed to α-PbO_(2)structure in space group Pbcn with lattice parameters of a=4.481 ?,b=5.578 A and c=4.921 A;(7) The exsolution inclusions of rutile from host ilmenite are mostly connected with an alternation process along the lamellar twinning plane of ilmenite induced by shockinduced high pressure and high temperature;(8) The P-T regime of 20-25 GPa and 1000 ℃ estimated for the Suizhou unmelted rock is suitable for phase transition of rutile into TiO_(2)-Ⅱ phase.

Radiological and X-Ray Diffraction Characterization of Bauxite and Rutile Ore Contaminated Environment in Kanam and Wase Mineral Exploration Sites, Plateau State-Nigeria

Two non-destructive analytical techniques (gamma spectrometer and X-ray diffractometer) were employed in the analysis of bauxite and rutile ore and their vicinity soil and control sourced within the Kanam and Wase mineral exploration sites. The activity concentrations of natural radionuclides 238U, 232Th, and 40K in the soil samples received from bauxite and rutile mineral mining vicinities revealed high concentrations of 238U, 232Th, and 40K compared to the control soil samples sourced 500 m away from the mineral exploration vicinities. Radiological detriments RLI, AUI, Hin and Hex unveiled values exceeding the radiation standard concentration (>1) for soil. X-ray diffraction characterization of bauxite ore revealed the interlocking minerals of Bauxite (18)%, Albite (11)%, Garnet (15)%, Illite (6)% and Muscovite (43)% in various proportions obtained within the 2θ range (9.18 to 64.4) and a peak value (intensity, cps) of 3400. Pure bauxite percentage in the ore meets metallurgical grade (15 - 25)%. X-ray diffraction of rutile ore revealed the minerals of rutile (40)%, quartz (21.4)%, ilmenite (27)% and garnet (11.8)% found within the 2θ range (27.5 to 35.6) and a peak value intensity of 31.1 - 100.0 cps also meeting the metallurgical grade of 15% - 25%. The major environmental concern associated with the mineral-sands industry is the radiation hazards, pollution of ground-water sources from heavy metals, mineral transport with heavy equipment’s, dredging operations in fragile coastal area and clearing of vegetation.

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）.

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.

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）.

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.

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.

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.

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.

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.

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.