Active Sites for Adsorption and Reaction of Molecules on Rutile TiO2(110) and Anatase TiO2(001) Surfaces (cited: 1)

The reactivity of specific sites on rutile TiO₂(110)-(1×1) surface and anatase TiO₂(001)-(1×4) surface has been comparably studied by means of high resolution scanning tunneling microscopy. At the rutile TiO₂(110)-(1×1) surface, we find the defects of oxygen vacancy provide distinct reactivity for O₂ and CO₂ adsorption, while the terminal fivefold-coordinated Ti sites dominate the photocatalytic reactivity for H₂O and CH₃OH dissociation. At the anatase TiO₂(001)-(1×4) surface, the sixfold-coordinated terminal Ti sites at the oxidized surface seem to be inert in both O₂ and H₂O reactions, but the Ti-rich defects which introduce the Ti³⁺ state into the reduced surface are found to provide high reactivity for the reactions of O₂ and H₂O. By comparing the reactions on both rutile and anatase surfaces under similar experimental conditions, we find the reactivity of anatase TiO₂(001) is actually lower than rutile TiO₂(110), which challenges the conventional knowledge that the anatase (001) is the most reactive TiO₂ surface. Our findings could provide atomic level insights into the mechanisms of TiO₂ based catalytic and photocatalytic chemical reactions.     

Hydrothermal synthesis and enhanced photocatalytic activity of mixed-phase TiO2 powders with controllable anatase/rutile ratio

In this study, mixed-phase TiO₂ powders were novelly synthesized via a facile and mild hydrothermal method without any post-heat treatment. TiOSO₄ and peroxide titanic acid (PTA) were used as inorganic titanium sources, while no special solvent or additive were introduced. The XRD and TEM results showed the mixed-phase TiO₂ powders were composed of anatase and rutile phases, and the PTA sol played an important role on forming the rutile nucleus. The proportion of rutile in the mixed-phase TiO₂ could be easily controlled in the range of 0%–70.5% by changing the amount of PTA sol used in the synthesis process. The UV-Visible absorption spectra indicated the prepared mixed-phase TiO₂ showed enhanced visible light absorption with the increase of rutile ratio. The photodegradation experiments revealed the mixed-phase TiO₂ exhibited the best photocatalytic activity at the rutile ratio of 41.5%, while a higher or lower rutile ratio both resulted in the decrease of photocatalytic activity.     

Phase composition and magnetic properties of niobium-iron codoped TiO2 nanoparticles synthesized in Ar/O2 radio-frequency thermal plasma

Nanoparticles of Nb⁵⁺-Fe³⁺ codoped TiO₂ with various Nb⁵⁺ concentrations (Nb/(Ti+Fe+Nb)=0-10.0 at%) and Fe³⁺ (Fe/(Ti+Fe+Nb)=0-2.0 at%) were synthesized using Ar/O₂ thermal plasma. Dopant content, chemical valence, phase identification, morphology and magnetic properties were determined using several characterization techniques, including inductively coupled plasma-optical emission spectrometer, X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis diffuse reflectance spectrometer, field-emission scanning electron microscopy, transmission electron microscopy and SQUID commercial instrument. The XRD revealed that all the plasma-synthesized powders were exclusively composed of anatase as major phase and rutile. The rutile weight fraction was increased by the substitution of Fe³⁺ for Ti⁴⁺ whereas it was reduced by the Nb⁵⁺ doping. The plasma-synthesized Nb⁵⁺-Fe³⁺ codoped TiO₂ powders had intrinsic magnetic properties of strongly paramagnetic and feebly ferromagnetic at room temperature. The ferromagnetic properties gradually deteriorated as the Fe³⁺ concentration was decreased, suggesting that the ferromagnetism was predominated by the phase composition as a carrier-mediated exchange.     

A sol–gel combustion synthesis method for TiO<Subscript>2</Subscript> powders with enhanced photocatalytic activity

TiO₂ photocatalytic powders were synthesized by a sol–gel combustion synthesis method in which urea was used as the fuel and titanyl nitrate was used as the oxidizer. Various fuel-to-oxidizer ratios were studied for their effects on the combustion phenomena and the properties of the synthesized TiO₂. The fuel-to-oxidizer ratio was found to determine the maximum combustion temperature, which in turn affects the specific surface area, crystallite size, and weight fraction of anatase phase of the synthesized TiO₂. The synthesized TiO₂ all contain carbonaceous species and are either pure anatase or anatase–rutile mixed phase in crystalline structure. The photocatalytic activity of the TiO₂ was found to correlate to a certain degree with the specific surface area, crystallite size, weight fraction of anatase phase, and visible and IR absorbances. The mixed phase TiO₂ shows a higher photocatalytic activity than the pure anatase phase TiO₂ when containing a small fraction (<~25 wt%) of rutile phase but a lower phoyocatalytic activity when containing a large fraction (>~25 wt%) of rutile phase. The synthesized TiO₂ all show higher photocatalytic activity than Degussa P25 TiO₂. The enhanced photocatalytic activity was attributed mainly to sensitization by the carbonaceous species and larger amounts of hydroxyl group adsorbed on the TiO₂ surface.     

Influence of transition metal-doped titanium(IV) dioxide on the photodegradation of polyethylene

The effects of adding dispersed powders of various forms of titanium(IV) dioxide on the photodegradation of polyethylene have been examined from the following points of view: effect of crystal form, concentration of pigment, transition metal ion, dopant concentration, calcination temperature of pigment, and pigment coating.The rate of photodegradation of polyethylene is reduced by adding certain grades of TiO₂ such as coated TiO₂ particles or TiO₂ doped with small percentages of Cr or Mn ions. The rate is increased on adding TiO₂ doped with V and especially Mo or W ions. The anatase form of TiO₂ is more photoactive than the rutile form, and the effect of increasing the calcination temperature of the pigment is to reduce photoactivity by boosting the rutile fraction. The concentration dependences of the degradation rates are complex, but can be directly related to the percentage of anatase achieved after calcination. Even the most aggressive of the metal-doped pigments are less photoactive than the Degussa P25 material, containing both rutile and anatase.     

Preparation of nanocrystalline TiO<Subscript>2</Subscript> powders for photocatalytic oxidation of phenol

Nanocrystalline TiO₂ powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl₄ solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m²/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO₂ nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO₂ powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO₂ (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO₂ crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO₂ photocatalysts of larger crystallite size.     

Titania nanotubes (TNTs) prepared through the complex compound of gallic acid with titanium; examining photocatalytic degradation of the obtained TNTs

It was for the first time that the complex compound of gallic acid with titanium (IV) salt was used as a precursor to synthesize titania nanotubes. The study was separated into four main sections; (I) synthesizing the complex of titanium with gallic acid, (II) synthesizing anatase and rutile phases through thermal decomposing of the complex, (III) investigating the possibility to synthesize titania nanotubes from the rutile and anatase phases, and (IV) photocatalytic ability of all the nanoparticles.Different methods were applied to analysis, including X-ray diffraction, 1H NMR, FT-IR spectroscopy, elemental analysis, quantum-chemical modeling, Raman spectroscopy, thermal analysis, photoluminescence, BET analysis (to investigate the specific surface activity, total pore volume), EDX, electron microscopy (SEM), acceleration voltages, electrical conductivity, BJH method (to determine average pore diameter), and UV-Vis spectroscopy.We illustrated the possibility of the synthesis of the titania nanotubes from the anatase phase, while rutile phase was not turned to a tube shape.The photocatalytic ability of the obtained nanoparticles was tested by degrading bromophenol blue, as an organic pollutant, under weak light. TiO₂ in the form of nanotubes could reduce the concentration of bromophenol blue to 82%, as well as the rutile phase - to 70%, and finally anatase as nan-spheres to 36%.     

The influence of titanium dioxide phase composition on dyes photocatalysis

A comparative study of TiO₂ powders prepared by sol–gel methods is presented. Titanium tetraisopropoxide was used as the precursor for the sol–gel processes. The effects of the annealing treatment on phase, crystallite size, porosity and photodegradation of dyes (methyl orange and methylene blue) were studied. The phase structure, microstructure and surface properties of the films were characterized by using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The X-ray diffraction was used for crystal phase identification, for the accurate estimation of the anatase–rutile ratio and for the crystallite size evaluation of each polymorph in the samples. It was found that the only TiO₂ anatase phase of the synthesized TiO₂ develops below 500 °C, between 600 and 800 °C the anatase coexist with rutile and above 800 °C only the rutile phase was found in the samples. Attention has been paid not only to crystal structures, but also to the porosity, the particle size and the photocatalytic properties. However, the annealing temperature was found to have significant influence on the photocatalytic properties. Different TiO₂ doctor blade thin films were obtained mixing the sol gel powder (100% anatase) and TiO₂ Aldrich with TiO₂ Degussa P25. The surfactant (Triton X100 or sodium dodecyl sulfate) affects the packing density of the particles during deposition and the photocatalytic degradation efficiency of the dyes. The photocatalytic degradation kinetics of methyl orange and methylene blue using TiO₂ thin film were investigated.     

Photocatalytic Crystalline and Amorphous TiO2 Nanotubes Prepared by Electrospinning and Atomic Layer Deposition

In this work core/shell composite polymer/TiO₂ nanofibers and from those TiO₂ nanotubes were prepared. First, poly(vinyl alcohol) (PVA) and poly(vinylpyrrolidone) (PVP) fibers were synthetized by electrospinning. They were covered with a 100 nm thick amorphous TiO₂ layer by atomic layer deposition at 50 °C. Later the polymer core was removed by two different methods: dissolution and annealing. In the case of dissolution in water, the as-prepared TiO₂ nanotubes remained amorphous, while when annealing was used to remove the polymers, the TiO₂ crystallized in anatase form. Due to this, the properties of amorphous and crystalline TiO₂ nanotubes with exactly the same structure and morphology could be compared. The samples were investigated by SEM-EDX, ATR-IR, UV-Vis, XRD and TG/DTA-MS. Finally, the photocatalytic properties of the TiO₂ nanotubes were studied by decomposing methyl-orange dye under UV light. According to the results, crystalline anatase TiO₂ nanotubes reached the photocatalytic performance of P25, while amorphous TiO₂ nanotubes had observable photocatalytic activity.     

A Rutile TiO2 Electron Transport Layer for the Enhancement of Charge Collection for Efficient Perovskite Solar Cells

Interfacial charge collection efficiency has demonstrated significant effects on the power conversion efficiency (PCE) of perovskite solar cells (PSCs). Herein, crystalline phase‐dependent charge collection is investigated by using rutile and anatase TiO₂ electron transport layer (ETL) to fabricate PSCs. The results show that rutile TiO₂ ETL enhances the extraction and transportation of electrons to FTO and reduces the recombination, thanks to its better conductivity and improved interface with the CH₃NH₃PbI₃ (MAPbI₃) layer. Moreover, this may be also attributed to the fact that rutile TiO₂ has better match with perovskite grains, and less trap density. As a result, comparing with anatase TiO₂ ETL, MAPbI₃ PSCs with rutile TiO₂ ETL delivers significantly enhanced performance with a champion PCE of 20.9 % and a large open circuit voltage (V_OC) of 1.17 V.     

Relationship Between Photocatalytic Activity and Structure of TiO2 Thin Film

TiO2 thin films with different crystalline structures were prepared by the CVD method. The relationship between photocatalytic activity of a TiO2 thin film and its crystalline type was investigated. These films were characterized by XRD and AFM. Their photocatalytic properties were tested by the degradation of NO2-. The results showed that the crystalline structures of TiO2 thin films are primary anatase and/or rutile when the preparation temperatures were less than 573 K and higher than 773 K respectively. When the preparation temperature was around 623 K, the structures of TiO2 thin films were mixed crystalline structure, which showed the highest catalytic activity. When the ratio of rutile to anatase in TiO2 thin films fell between 0.5 and 0.7, the highest catalytic activity for the degradation of NO2- was found.     

Crystallization kinetics study of In-doped and (In-Cr) co-doped TiO2 nanopowders using in-situ high-temperature synchrotron radiation diffraction

The influence of TiO₂ nanopowder doping with 4 wt% indium and 2 wt% each of indium and chromium on phase transformation was studied. Samples were heated from ambient temperature to 950 °C in sealed quartz capillaries, and in-situ synchrotron radiation diffraction measurements were obtained. Capillary sealing yielded an increase in capillary gas pressure to 0.42 MPa at 950 °C in proportion to absolute temperature by Gay-Lussac’s Law. The initial synthesized samples were amorphous, and crystalline anatase appeared at 200 °C. Crystalline rutile appeared at 850 °C for the nanomaterials that were doped with In and In and Cr. A change in sealed-capillary oxygen partial pressure yielded a decrease and an increase in crystallization temperature, respectively, for the amorphous-to-anatase and anatase-to-rutile transformations. Crystalline titania (anatase and rutile) formed from the amorphous titania by 800 °C and 900 °C, for materials doped with In and In-Cr, respectively. The anatase concentration that was dominant in the In-doped materials up to 950 °C and the higher rutile concentration for the In-Cr doped materials from 900 to 950 °C results from the defect structure that was induced by doping. Cr-ions in the Ti sub-lattice retarded the transformation of anatase to rutile when compared with the retarding effect of mixed In/Cr ions. The transformation results because of the relatively smaller radius of Cr-ions when compared with the In-ions. The differences in phase-transformation kinetics for In, In-Cr and for undoped nanopowders in the literature agree with the calculated transformation activation energies.     

TiO2纳米粒子制备方法对其光催化活性的影响

分别用胶溶法、金属醇盐水解法和低温水解法制备了TiO2纳米粒子;采用XRD和BET技术,测试了TiO2粒子的粒径、晶型及表面积。以庚烷的气相光催化氧化为探针反应,考察了不同方法、不同温度处理的TiO2粒子的光催化活性。结果表明,以胶溶法和金属醇盐水解法制备的TiO2粒子,随焙烧温度的增加TiO2粒子长大,晶型由锐钛矿向金红石型转变,光催化活性降低。用低温水解法,可在低温下制得金红石型TiO2粒子,但其催化活性很低。说明由原料和制备方法所决定的TiO2粒子的物理化学性质,影响其光催化行为。锐钛矿型TiO2粒子催化活性较金红石型TiO2好。这是由于前者的表面羟基含量较高且带隙能较大的缘故。     

Remarkable Charge Separation and Photocatalytic Efficiency Enhancement through Interconnection of TiO2 Nanoparticles by Hydrothermal Treatment

Although tremendous effort has been directed to synthesizing advanced TiO₂, it remains difficult to obtain TiO₂ exhibiting a photocatalytic efficiency higher than that of P25, a benchmark photocatalyst. P25 is composed of anatase, rutile, and amorphous TiO₂ particles, and photoexcited electron transfer and subsequent charge separation at the anatase–rutile particle interfaces explain its high photocatalytic efficiency. Herein, we report on a facile and rational hydrothermal treatment of P25 to selectively convert the amorphous component into crystalline TiO₂, which is deposited between the original anatase and rutile particles to increase the particle interfaces and thus enhance charge separation. This process produces a new TiO₂ exhibiting a considerably enhanced photocatalytic efficiency. This method of synthesizing this TiO₂, inspired by a recently burgeoning zeolite design, promises to make TiO₂ applications more feasible and effective.     

Degradation of organic compounds on TiO<Subscript>2</Subscript> photocatalysts prepared by a hydrothermal method in the presence of NH<Subscript>4</Subscript>F

TiO₂ photocatalysts were synthesized by a hydrothermal method from tetraisopropyl orthotitanate (TPOT) in the presence of NH₄F with different NH₄F/Ti molar ratios (0, 0.25, and 1). The formation of a well-crystallized anatase phase of TiO₂ and the suppression of phase transition to rutile were observed, even at high calcination temperature, owing to the effects of NH₄F. The TiO₂ synthesized hydrothermally with NH₄F exhibited absorption with a shift to the longer wavelengths of the visible-light region. The hydrothermally synthesized TiO₂ with a moderate amount of NH₄F exhibited high photocatalytic activity for the degradation of alcohol diluted in water under both UV-light and visible-light irradiations.     

Curious behaviors of photogenerated electrons and holes at the defects on anatase,rutile, and brookite TiO2 powders: A review

Photocatalytic reactions are governed by photogenerated charge carriers upon band gap excitation. Therefore, for better understanding of the mechanism, the dynamics of photocarriers should be studied. One of the attractive materials is TiO₂, which has been extensively investigated in the field of photocatalysis. This review article summarizes our recent works of time-resolved visible to mid-IR absorption measurements to elucidate the difference of anatase, rutile, and brookite TiO₂ powders. The distinctive photocatalytic activities of these polymorphs are determined by the electron-trapping processes at the defects on powders. Powders are rich in defects and these defects capture photogenerated electrons. The depth of the trap is crystal phase dependent, and they are estimated to be < 0.1 eV, ∼0.4 eV and ∼0.9 eV for anatase, brookite, and rutile, respectively. Electron trapping reduces probability to meet with holes and then elongate the lifetime of holes. Therefore, it works negatively for the reaction of electrons but positively works for the reaction of holes. In the steady-state reactions, both electrons and holes should be consumed. Hence, the balance between the positive and negative effects of defects determines the distinctive photocatalytic activities of anatase, rutile, and brookite TiO₂ powders.     

Study on the formation of H2O2 on TiO2 photocatalysts and their activity for the photocatalytic degradation of X-GL dye

Titanium dioxide (TiO₂) nanoparticles of both anatase and rutile phases were synthesized by hydrothermal treatment of microemulsions, and their photocatalytic activity for the degradation of X-GL dye was investigated. The only difference between the two methods used was that different acids were added to the microemulsions to make a direct comparison of the photocatalytic activity of the polymorphs possible. UV — Vis reflectance and XRD spectroscopic investigations of these titanium dioxides indicated that a rutile structure could be formed (PR) when hydrochloric acid was used, and anatase formed (PA) when nitric acid was used. The activity of the two polymorphs and P-25 for the photocatalytic degradation of dye in water was also examined. It was found that P-25 consisting of anatase and rutile has the highest activity, and PR consisting of rutile has the lowest. Photodegradation of X-GL in the presence of these different TiO₂ particles under air-equilibrated controlled conditions led to the formation of hydrogen peroxide. The formation rate of H₂O₂ depended on the difference in crystalloid phase. These results indicate that the observed differences in the photocatalytic activity for the three TiO₂ photocatalysts are directly related to the formation rate of H₂O₂.     

水热法合成掺杂铁离子的小管径TiO2纳米管

碳纳米管这种一维结构的新材料的发现为物理、化学、材料科学和纳米科学开辟了全新的研究领域.近年来,非碳无机类富勒烯(Inorganic Fullerenelike,简称IF)纳米管也受到人们的广泛关注.     

Thermal conductivity of dry anatase and rutile nano-powders and ethylene and propylene glycol-based TiO2 nanofluids

Thermal conductivity behaviour was studied for two TiO₂ nano-powders with different nanocrystalline structures, viz. anatase and rutile, as well as nanofluids formulated as dispersions of these two oxides up to volume concentrations of 8.5% in two different glycols, viz. ethylene and propylene glycol. Because it is known that titanium dioxide can exhibit three different crystalline structures, the dry nano-powders were analysed using X-ray Diffraction to determine the nanocrystalline structure of the powders. Two different techniques were employed in the thermal conductivity study of the materials. Dry nano-powders, with and without compaction, were analysed at room temperature by using a device based on the guarded heat flow meter method. Nanofluids and base fluids were studied with a transient hot wire technique over the temperature range from (283.15 to 343.15) K. The base fluid propylene glycol was measured by using both techniques in order to verify the good agreement between both sets of results. The experimental measurements presented in this work were compared with other literature data for TiO₂ nanofluids in order to understand the thermal conductivity enhancement as a function of nanoparticle concentration. Different theoretical or semi-theoretical approaches such as Maxwell, Peñas et al., Yu-Choi were evaluated comparing with our experimental values. A parallel model was used to predict thermal conductivities employing experimental values for dry nanopowder.     

Estimation of phase ratio for nano-sized TiO2 powders by Ti K-edge XANES

We estimated the crystallinity and phase ratio of anatase to rutile in TiO₂ nano-particles by Ti K-edge X-ray absorption near-edge spectroscopy (XANES) spectra. The nano-sized TiO₂ powders prepared by the homogeneous precipitation process at low temperature (HPPLT) were compared with the commercial TiO₂ powders with good crystallinity. From the comparison with the experimental and calculated Ti K-edge XANES spectra, we found the possibility of efficient estimation in the crystallinites and the phase ratio of anatase to rutile for nano-sized TiO₂ mixtures.