Electronic Structure and Size of TiO2 Nanoparticles of Controlled Size Prepared by Aerosol Methods

Summary.  A complete characterization of nanostructures has to deal both with electronic structure and dimensions. Here we present the characterization of TiO₂ nanoparticles of controlled size prepared by aerosol methods. The electronic structure of these nanoparticles was probed by X-ray absorption spectroscopy (XAS), the particle size by atomic force microscopy (AFM). XAS spectra show that the particles crystallize in the anatase phase upon heating at 500°C, whereas further annealing at 700°C give crystallites of 70% anatase and 30% rutile phases. Raising the temperature to 900°C results in a complete transformation of the particles to rutile. AFM images reveal that the mean size of the anatase particles formed upon heating at 500°C is 30 nm, whereas for the rutile particles formed upon annealing at 900°C 90 nm were found. The results obtained by these techniques agree with XRD data. Received October 5, 2001. Accepted (revised) December 6, 2001     

High temperature stability and photocatalytic activity of nanocrystalline anatase powders with Zr and Si co-dopants

TiO₂ nanopowders doped by Si and Zr were prepared by sol–gel method. The effects of Si and Zr doping on the structural, optical, and photo-catalytic properties of titania nanopowders have been studied by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a significant effect on anatase phase stability, crystallinity, and particle size of TiO₂. Titania rutile phase formation in ternary system (Ti–Si–Zr) was inhibited by Zr⁴⁺ and Si⁴⁺ co-doped TiO₂ in high temperatures (500–900 °C) and 36 mol% anatase composition is retained even after calcination at 1,000 °C. The photocatalyst activity was evaluated by photocatalytic degradation kinetics of aqueous methylen orange under visible radiation. The results show that the photocatalytic activity of the 20 %Si and 15 %Zr co-doped TiO₂ nanopowders have a larger degradation efficiency than pure TiO₂ under visible light.     

Thermal behaviour of titanium dioxide nanoparticles prepared by precipitation from aqueous solutions

Thermogravimetry-differential thermal analysis, emanation thermal analysis, mass spectrometry detection, Fourier transform infrared and XRD were used to characterize thermal behaviour of titanium dioxide photocatalyst precursors prepared by precipitation at various conditions from peroxotitanic acid sols. The transmission electron microscopy HRTEM technique was used to characterize the surface microstructure. The sols contained TiO₂ anatase particles of approximately 10 nm in diameter. During heating of the air dried samples, their chemical degradation took place giving rise to anatase. On further heating, the crystallization of anatase and formation of rutile phase was observed. To test the photocatalytic activity of the samples, the decomposition of 4-chlorophenol (4-CP) under ultraviolet and visible irradiation was monitored. It was shown that photocatalytic activities of the samples are comparable to the Degussa P25 photocatalyst reference material.     

Morphological and phase evolution of TiO2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

Nanosized anatase and rutile TiO₂ having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H₂O₂) in water/isopropanol media by a facile sol-gel process. The TiO₂ nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO₂ are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.     

Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co‐Catalyst

The high‐pressure hydrogenation of commercially available anatase or anatase/rutile TiO₂ powder can create a photocatalyst for H₂ evolution that is highly effective and stable without the need for any additional co‐catalyst. This activation effect cannot be observed for rutile; however, for anatase/rutile mixtures, a strong synergistic effect can be found (similar to results commonly observed for noble‐metal‐decorated TiO₂). EPR and PL measurements indicated the intrinsic co‐catalytic activation of anatase TiO₂ to be due to specific defect centers formed during hydrogenation. These active centers can be observed specifically for high‐pressure hydrogenation; other common reduction treatments do not result in this effect.     

三维大孔TiO2光催化剂的制备及其催化性能

 以聚甲基丙烯酸甲酯微球为模板,以钛酸正丁酯为原料,采用溶胶-凝胶法制备了具有三维结构的大孔TiO2. 采用差示扫描量热、热重-微分热重、X射线衍射、红外光谱、扫描电子显微镜和氮气吸附等手段对样品进行了表征. 结果表明,高温热处理后得到的三维大孔TiO2光催化剂的孔径为200 nm左右,孔径分布均匀, TiO2纳米晶粒中锐钛矿相和金红石相的含量分别为82%和18%. 光催化氧化实验表明,此种三维结构的TiO2对甲基橙溶液具有较好的光催化氧化性能.     

Thermal and hydrothermal stability of flame hydrolytically synthesized SiO2/TiO2 mixed oxides

The phase stability of the two TiO₂ modifications (anatase and rutile) in fumed SiO₂/TiO₂ nano-composites (0–24.8 wt-% silica) under thermal and hydrothermal conditions was investigated by X-ray powder diffraction, transmission electron microscopy (TEM) and gas adsorption methods (BET). The results show that the phase transformation from anatase to rutile type of structure and the growth of anatase crystallites are significantly retarded by mixing small amounts of SiO₂ into TiO₂, while the specific surface area is maintained. The SiO₂/TiO₂-composites reveal a remarkable shift in the anatase to rutile transformation temperature from approx. 500 °C (pure TiO₂) to approx. 1000 °C (samples with SiO₂ contents of more than 10%). The rate of phase transformation from anatase to rutile is enhanced under hydrothermal conditions compared to conventional thermal treatment, e.g. pure titania (AEROXIDE^® TiO₂ P25) annealed under hydrothermal conditions (100 g/m³ absolute humidity, 4 h at 600 °C) had a rutile content of 85%, while the same specimens annealed in absence of humidity contained only 46% rutile. However, the difference in rate of phase transformation became less pronounced when the silica content in SiO₂/TiO₂-composites was further increased.TEM results showed that the surface of the anatase crystallites was covered with silica. This averts coalescence of anatase crystallites and keeps them under a critical size during the annealing process. When the crystal domains grew larger, a rapid conversion to rutile took place. The critical size of anatase crystallites for the phase transformation was estimated to be 15–20 nm.     

Enhanced Photoactivity in Bilayer Films with Buried Rutile–Anatase Heterojunctions

Herein, we study the photoactivity of anatase–rutile bilayer thin films consisting of an anatase overlayer of variable thickness from some tenths to some hundred nanometers deposited onto a rutile thin film. As references single anatase layers of equivalent thickness were deposited onto silicon. All the films were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. The photoactivity of the samples was assessed by following the evolution with the UV illumination time of both the wetting angle on the thin film surface and the decoloration of a dye in a water solution. While a similar efficiency is found for the first type of experiments irrespective of the anatase thickness, in the second type a maximum in the photoactivity is found for a thickness of the anatase layer of about 130 nm. This enhanced photoactivity in bilayer systems with a buried anatase–rutile heterojunction is related to the formation of different Schottky potential barriers in the anatase layer, depending on its thickness and the substrate (i.e. rutile or SiO₂) where it is deposited.     

二氧化钛与针铁矿复合光催化材料的制备与光催化性能

以四氯化钛为钛源,针铁矿(α-FeOOH)为载体,采用水解沉淀法制备了金红石相二氧化钛(Ti₂O)与α-FeOOH的复合光催化材料,并采用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线能量散射谱和X射线光电子能谱对样品进行了表征.结果表明,低温下,金红石相Ti₂O包覆于α-FeOOH表面,并形成复合结构;较高温下,铁离子进入金红石相Ti₂O晶格,并形成铁掺杂金红石相Ti₂O纳米管;中温下,样品兼有复合和掺杂两者特征.在室温下以甲基橙为降解对象,采用钨灯+氘灯(波长200~800nm)为光源,对样品的光催化活性进行了测试.结果表明,样品对甲基橙的光催化降解效果良好;与纯α-FeOOH和金红石相Ti₂O相比,不同结构样品的光催化活性均有所提高,其中,复合兼掺杂型样品的光催化活性最高.由此可见,与α-FeOOH复合和铁掺杂是提高Ti₂O光催化活性的有效途径.     

Synergistic effect between TiO2 sol–gel and Degussa P25 in dye photodegradation

The TiO₂ powders were synthesized by versatile and low cost sol–gel process using HNO₃ and titanium tetra-isopropoxide (volumetric ratio of 4:1) following by the hydrolysis reaction. The powders show the two polymorphs of TiO₂: 96 % anatase and 4 % brookite, due to acidic condition (pH = 3). Thin films of titanium oxide were obtained by dip-coating, using the sol–gel of titanium oxide mixed with commercial Degussa P25 into a weight ratio 1:1 or 1:1.5, to enhance the synergistic effect of anatase/rutile ratio aiming at increasing the efficiency of the TiO₂ photocatalyst in dyes degradation. The thin film surface (charge and morphology) was controlled by polymer (poly-ethylene glycol) and surfactant (Sodium dodecyl sulphate, Triton X100) addition. The titanium oxide was characterized by particle size analyzer, contact angle measurements, X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic properties of powders and coatings were evaluated based on the degradation efficiency of two reference dyes (methyl orange and methylene blue). The results outline that poly(ethylene glycol) and films morphologies are the most influential factors that affecting the photocatalytic activity.     

Versatile biomimetic dendrimer templates used in the formation of TiO2 and GeO2

Biomimetic synthesis is emerging as an advantageous alternative to the harsh synthetic conditions traditionally used in metal oxide syntheses techniques. Silaffins, proteins from the C. fusiformis diatom, form silica in an aqueous environment under benign conditions. Amine terminated PAMAM and PPI dendrimers are effective mimics of silaffins and other silica precipitating polyamines. We have expanded the scope of dendrimer mediated metal oxide formation to include titanium dioxide, a photocatalyst, and germanium dioxide, a blue photoluminescent material. The nanoparticles were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (IR), and X-ray diffraction patterns (XRD). A variable temperature XRD analysis of TiO(2) nanoparticles was conducted to study the transition from anatase to rutile. TiO(2) nanoparticles synthesized in phosphate buffer showed a 200 degrees C decrease in the anatase to rutile transition temperature relative to TiO(2) templated in water. XRD analysis of GeO(2) nanoparticles in either water or phosphate buffer reveal crystalline alpha-phase germanium oxide. To our knowledge, this is the first report of the synthesis of crystalline GeO(2) under ambient conditions.     

DSC investigation of nanocrystalline TiO<Subscript>2</Subscript> powder

The aim of the article is to investigate the influence of particle size on titanium dioxide phase transformations. Nanocrystalline titanium dioxide powder was obtained through a hydrothermal procedure in an aqueous media at high pressure (in the range 25–100 atm) and low temperature (≤200 °C). The as-prepared samples were characterized with respect to their composition by ICP (inductive coupled plasma), structure and morphology by XRD (X-ray diffraction), and TEM (transmission electron microscopy), thermal behavior by TG (thermogravimetry) coupled with DSC (differential scanning calorimetry). Thermal behavior of nanostructured TiO₂ was compared with three commercial TiO₂ samples. The sequence of brookite–anatase–rutile phase transformation in TiO₂ samples was investigated. The heat capacity of anatase and rutile in a large temperature range are reported.     

Selective dissolution of TiO2 crystalline phases: Physicochemical characterization and photocatalytic activity

In this study, different commercially available TiO₂ powders (Degussa P25, pure anatase, and rutile) were submitted to selective dissolution treatments, with H₂O₂/NH₄OH and 10% HF, known to remove rutile and anatase from physical mixtures. The aim was to check whether a particular separation method designed to remove a specific crystalline phase influences the properties of the other phase from the mixture or not. More precisely, we have studied how the HF dissolution method designed to selectively remove the anatase affected the physicochemical and photocatalytic properties of rutile. In a similar way, the changes in the anatase properties were studied, after the H₂O₂/NH₄OH treatment, initially used to remove rutile from the mixture. All the samples were characterized by X-ray diffraction, nitrogen adsorption–desorption, transmission electron microscopy, diffuse reflectance (DR) ultraviolet–visible, and Raman spectroscopy. The photocatalytic activity of these powders was tested in the oxidation of p-chlorophenol from water. The selective treatment methods not only dissolved the target phase but also changed some physicochemical and the photocatalytic performances of the other TiO₂ crystalline phase in a considerable manner. These aspects should be taken into account in the studies regarding the synergistic effects of anatase and rutile, especially in reconstructed TiO₂ photocatalysts.     

Conducting polyaniline-rutile TiO2 nanocomposites for the development of high-k dielectric materials

Inorganic dielectrics encapsulated in an organic matrix are showing excellent promise as novel dielectric materials. In this work, firstly highly organized crystalline nanoparticles of rutile TiO₂ were synthesized by acid hydrolysis of titanium isopropoxide at room temperature. Then we developed a novel dielectric material consisting of highly organized rutile TiO₂/polyaniline (PAni) nanocomposites by in-situ chemical oxidative polymerization. The structural, morphological, conducting, and dielectric properties of the rutile TiO₂/PAni nanoparticles have been evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution-transmission emission microscopy (HR-TEM), four-point probe technique, CV (Capacitance versus Voltage), and Impedance analyzer. The nanocomposites show 70 times higher permittivity compared to rutile nanoparticles and much higher compared to anatase/PAni (ES) nanocomposites at 10 MHz. Large interfacial polarizations, nanostructure, and dopant levels are the key factors for the large dielectric constant of the nanocomposites. The rutile/PAni (ES) nanocomposites might see potential uses in super-capacitors, gate dielectric in transistors, and capacitive-type gas sensors.     

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.     

Synthesis and electrorheology of rod-like titanium oxide particles prepared via microwave-assisted molten-salt method

The rod-like titanium dioxide (TiO₂) particles were synthesized by a simple and rapid microwave-assisted molten-salt method. The X-ray diffraction analysis revealed the phase composition transformation from the anatase phase of original TiO₂ nanomaterial to the rutile phase of high crystallinity. Scanning electron microscopy proved the conversion of originally globular particles of original anatase TiO₂ sized from 200 to 500 nm into rods with a length of 5–10 μm and a diameter between 0.5 and 2 μm. The electrorheological (ER) measurements performed under steady-state flow as a function of the applied electric field strength and particle concentration showed that suspended rutile rod-like TiO₂ particle-based fluid exhibits much higher ER activity than that of original anatase TiO₂ material powder. These observations were clearly demonstrated by viewing their dielectric spectra analyses.     

Stable Co‐Catalyst‐Free Photocatalytic H2 Evolution From Oxidized Titanium Nitride Nanopowders

A simple strategy is used to thermally oxidize TiN nanopowder (～20 nm) to an anatase phase of a TiO₂:Ti³⁺:N compound. In contrast to the rutile phase of such a compound, this photocatalyst provides activity for hydrogen evolution under AM1.5 conditions, without the use of any noble metal co‐catalyst. Moreover the photocatalyst is active and stable over extended periods of time (tested for 4 months). Importantly, to achieve successful conversion to the active anatase polymorph, sufficiently small starting particles of TiN are needed. The key factor for catalysis is the stabilization of the co‐catalytically active Ti³⁺ species against oxidation by nitrogen present in the starting material.     

Plasma-Assisted Synthesis of TiO2 Nanorods by Gliding Arc Discharge Processing at Atmospheric Pressure for Photocatalytic Applications

The present study explores a new method of synthesis of TiO₂ nano-particles in an aqueous medium from TiCl₃ precursor by non-thermal plasma in humid air as feeding gas obtained at atmospheric pressure. The precursor solution, TiCl₃ is oxidized by strongly reactive species generated by gliding arc plasma (HO^· = 2.85 V/SHE) to produce titanium oxide powders. The synthesized powder was characterised by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, nitrogen physisorption, and UV–Vis spectroscopy. The results obtained showed that the material consists of rod-shaped nanoparticles of rutile and anatase phases. The presence of TiO₂ phases was confirmed by FTIR spectrum and textural analyses showed that the material is mesoporous with specific surface area of 158 m² g^?1. UV–Visible spectrum of the plasma-synthesized TiO₂ sample showed that it absorbs in the UV–A region leading to effective use as a photocatalyst under visible light.     

Hierarchical chlorine-doped rutile TiO2 spherical clusters of nanorods: Large-scale synthesis and high photocatalytic activity

In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light (λ>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, ¹H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO₂ under visible light (λ>420 nm). These hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity.     

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%.