不同形貌TiO2的水热合成及对苯酚的降解研究

采用水热合成法, 通过对溶液的pH值、反应物配比、陈化温度及陈化时间等条件的控制, 合成出不同晶型及形貌的TiO2纳米粒子. 结果表明, 溶液的pH＝11, n(钛酸丁酯):n(三乙醇胺)＝1:2, 陈化温度为150 ℃, 陈化时间为48 h时, 能得到较规则的、长径比约为4:1的棒状TiO2. 当溶液pH<10时, 得到球形的TiO2纳米粒子; 陈化时间为24 h时, 得到纺锤形TiO2纳米晶. 以上合成的纳米粒子均为锐钛矿型, 但当溶液的pH>12时, 则得到板钛矿型TiO2粒子. 以苯酚为降解模型, 考察了不同形貌TiO2的光催化活性.     

Unusual crystallization behaviors of anatase nanocrystallites from a molecularly thin titania nanosheet and its stacked forms: increase in nucleation temperature and oriented growth

Crystallization behaviors of anatase nanocrystallites from an ultrathin two-dimensional reactant composed of exfoliated titania nanosheets have been studied by monitoring the heating process of their well-organized films, with which the film thickness can be controlled from a molecularly thin monolayer to a stacked multilayer structure with a stepwise increment of approximately 1 nm. The heated products were identified by means of total reflection fluorescence X-ray absorption near-edge structure analysis and in-plane X-ray diffraction measurements using a synchrotron radiation source. The films composed of five or more layers of stacked nanosheets were transformed into anatase at 400-500 degrees C, which is a normal crystallization temperature of anatase from bulk reactants. As the film became thinner by decreasing the number of nanosheet layers to five or less, the crystallization temperature was found to increase and finally reached 800 degrees C for the monolayer film. Interestingly, preferential growth of anatase along the c-axis was strongly promoted for these ultrathin films. These unusual behaviors may be understood in terms of crystallization from the two-dimensional system of scarcely distributed reactants. The titania nanosheet crystallite is much thinner than the unit cell dimensions of anatase, and therefore, extensive atomic diffusion is required for the transformation particularly for the ultrathin films with a critical number (2-3) of stacked nanosheet layers. There is some structural similarity between anatase and titania nanosheet, which may account for the oriented growth of anatase nanocrystallites.     

EPR investigation of TiO2 nanoparticles with temperature-dependent properties

An in situ electron paramagnetic resonance (EPR) study has been carried out for anatase (Hombikat UV100) and rutile TiO(2) nanoparticles at liquid helium (He) temperature (4.2 K) under UV irradiation. Rutile titania was synthesized by ultrasonic irradiation with titanium tetrachloride (TiCl(4)) as the precursor. XRD and Raman results evidence the crystallinity of titania phases. The nature of trapped electrons and holes has been investigated by EPR spectroscopy under air and vacuum conditions. Illumination of TiO(2) powder (anatase and rutile) at 4.2 K resulted in the detection of electrons being trapped at Ti(4+) sites within the bulk and holes trapped at lattice oxide ions at the surface. The stability of electron traps was very sensitive to temperature in both phases of TiO(2). The annealing kinetics of the EPR detected radicals has been studied from 4.2 K to ambient temperature and also for calcined titania particles from 523 to 1273 K.     

Nonhydrolytic synthesis of high-quality anisotropically shaped brookite TiO2 nanocrystals

A surfactant-assisted nonaqueous strategy, relying on high-temperature aminolysis of titanium carboxylate complexes, has been developed to access anisotropically shaped TiO2 nanocrystals selectively trapped in the metastable brookite phase. Judicious temporal manipulation of precursor supply to the reaction mixture enables systematic tuning of the nanostructure geometric features over an exceptionally wide dimensional range (30-200 nm). Such degree of control is rationalized within the frame of a self-regulated phase-changing seed-catalyzed mechanism, in which homogeneous nucleation, on one side, and heterogeneous nucleation/growth processes, on the other side, are properly balanced while switching from the anatase to the brookite structures, respectively, in a continuous unidirectional crystal development regime. The time variation of the chemical potential for the monomer species in the solution, the size dependence of thermodynamic structural stability of the involved titania polymorphs, and the reduced activation barrier for brookite nucleation onto initially formed anatase seeds play decisive roles in the crystal-phase- and shape-tailored growth of titania nanostructures by the present approach.     

Low‐Temperature Synthesis of Crystalline Inorganic/Metallic Nanocrystal‐Halloysite Composite Nanotubes

We have demonstrated a facile approach for the low‐temperature synthesis of crystalline inorganic/metallic nanocrystal‐halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic nanocrystals on halloysite nanotubes. The halloysite clay nanotubes can adsorb the target precursor and induce inorganic/metallic nanocrystals to grow in situ. The crystalline phase and morphology of the composite clay nanotubes is tunable. By simply tuning the acidity of the titania sol, the crystalline titania‐clay nanotubes with tunable crystalline phases of anatase, a mixture of anatase and rutile or rutile are achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate)‐halloysite composite nanotubes. Metallic nickel nanocrystal can also be grown on the surface of halloysite nanotubes at low temperature. The traditional thermal treatment for crystallite transformation is not required, thus intact contour of halloysite nanotubes and the crystallinity structure of halloysite nanotubes can be guaranteed. The combined properties from inorganic/metallic nanocrystal (high refractive index, high dielectric constant and catalytic ability) and the halloysite clay nanotubes are promising for applications such as photonic crystals, high‐k‐gate dielectrics, photocatalysis and purification.     

Synthesis of visible-light reactive TiO2−xNy photocatalyst by mechanochemical doping

Yellowish TiO_2−xN_y was prepared by a novel mechanochemical nitrogen-doping method. The samples were prepared by a high-energy ball milling of P25 titania with different nitrogen sources such as hexamethylenetetramine, urea or ammonium carbonate, followed by calcination in air at 400 °C. The high mechanical energy accelerated the phase transformation of anatase to rutile, while the existence of the nitrogen reagents tended to block the transformation. The calcination treatment slightly increased the crystallinity of the prepared titania. The prepared powders possessed two absorption edges at around 400 and 540 nm and showed an excellent photocatalytic ability for the oxidation of nitrogen monoxide under visible light irradiation. Under the irradiation of visible light with wavelengths of >510 nm, nitrogen monoxide could be continuously removed by the nitrogen doped titania prepared from the P25 titania-hexamethylenetetramine mixture, while the powders prepared using urea and ammonium carbonate as nitrogen sources showed lower activities. This mechanochemical technique might be widely useful for doping oxides with nonmetallic elements.     

Synthesis and characterization of nano titania powder with high photoactivity for gas-phase photo-oxidation of benzene from TiOCl(2) aqueous solution at low temperatures

Nano rutile, anatase, and bicrystalline (anatase + brookite) titania powders with an average crystal size of below 10 nm are prepared from aqueous TiOCl(2) solution at low temperatures by adjusting pH values of the starting solution and adding different additives. Adding a small amount of octyl phenol poly(ethylene oxide) into aqueous TiOCl(2) solution leads to the change of particle morphologies of obtained nano titania from needlelike to nano spherical rutile crystals. Amorphous-anatase transformation of titania could proceed in liquid-solid reaction at low temperatures, even at room temperature. A formation mechanism of rutile, anatase, and brookite titania was proposed. It is found that H(+) or H(3)O(+) plays a catalytic role in the phase transformation from amorphous to anatase titania and that the presence of a small amount of SO(4)(2)(-) ion is unfavorable to the formation of both rutile and brookite. By carefully adjusting preparation conditions, nano pure anatase with higher surface area, good crystallinity, and a lower recombination rate of photoexcited electrons and holes was obtained. This nano pure anatase showed a very good photocatalytic activity for gas-phase photo-oxidation of benzene.     

Effect of temperature on the action spectra of pristine and Cu-grafted titania

The dependence of action spectra for pristine and Cu-grafted anatase TiO₂ on temperature for photocatalytic acetone vapor oxidation at 40, 100 and 140 °C is described. The results obtained demonstrate the thermal inhibition of activity under UV irradiation for pristine titania at 140 °C, while for TiO₂ grafted with copper species this inhibition is suppressed. Photonic efficiency of visible radiation energy utilization by Cu-grafted titania increases with temperature and exceeds the corresponding value for pure anatase in the investigated temperature range.     

结晶二氧化钛多孔球的常压液相制备

利用沸水处理有机钛前驱体球较为便捷地制备出结晶二氧化钛多孔球,采用XRD、SEM和TEM对二氧化钛球进行表征,并探讨了二氧化钛球锐钛矿纳米晶形成以及形貌变化的机理。结果表明：延长沸水处理时间有利于多孔结构的形成和纳米粒子的晶化,随处理时间的增加,前驱体球表面变得越来越粗糙,二氧化钛结晶度也逐渐增强。其形成机理主要归因于沸水处理过程中有机钛前驱体球原位发生的完全水解和聚合。     

纳米TiO2低温水解法的晶型控制合成及其表面织构的研究

分别以TiCl₄，Ti(NO₃)₄和Ti(SO₄)₂为前驱体，在低温和强酸性条件下，通过水解反应可控地合成了具有不同晶相组成，且比表面积较高的纳米TiO₂，并用XRD，TEM和N₂^-吸附脱附技术对其晶相、粒径大小、形貌及比表面积进行了表征。结果表明，钛离子在有Cl^-、NO₃^-存在的酸性溶液中水解，水解温度≤80 ℃，可以生成结晶良好的具有细小晶粒尺寸和较高比表面积的金红石型纳米TiO₂粉体，水解温度>80 ℃，反而有锐钛矿型TiO₂生成，而在有SO₄^2-存在的酸性溶液中，TiO₂样品的晶相组成不随水解温度的变化而改变，均为锐钛矿型，其比表面积可达300 m²·g^-1。     

Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity

Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria.     

Study of the speciation of carbon-14 in the primary circuit of pressurized-water reactors

The work presented in this article relates to the chemical speciation of carbon-14 in the primary circuit of pressurized-water reactors (PWR). The thermodynamic diagrams for carbon under the operating conditions of the primary circuit of PWR were plotted using the CHNOSZ thermochemical code which uses the Hegelson–Kikham–Flowers (HKF) thermodynamic model. The obtained results were compared to the published data. In an operating PWR with the redox potential imposed in the primary fluid by the pair H₂/H₂O, methane appears to be the predominant form that should be present in the primary circuit. When the reactor is shut down (low temperature, oxidizing medium), the inorganic forms of carbon (carbonate, hydrogen carbonate) predominate.     

New continuous solid solution in the Zn<Subscript>2</Subscript>InV<Subscript>3</Subscript>O<Subscript>11</Subscript>–Mg<Subscript>2</Subscript>InV<Subscript>3</Subscript>O<Subscript>11</Subscript> system

In this study, mechanical activation process was used for intimate mixing as well as producing finely ground particles, increased surface area and improved chemical reactivity of milled materials for producing SrTiO₃ from commercially pure strontium carbonate and TiO₂ as a contributive process. Characterization of milled powder mixture by X-ray diffraction analysis showed that disappearing, decreasing and/or shifting of the patterns occurred with mechanical activation that means amorphization was taken place. Amorphization was also demonstrated by FT-IR analysis where shift of band centers as well as the decrement of transmittance related to CO₃ was observed. Advantage of amorphization was established with high-temperature XRD analysis which showed 1300 °C was not enough for non-activated mixture to form SrTiO₃, whereas structure only composed of SrTiO₃ at 1000 °C for activated ones. The reason for this phenomenon was investigated by DTA-TG analysis, and it was based on energy accumulation originated from mechanical activation that corresponds to peak temperature shifting to the lower temperatures and CO₂ liberation at mechanical activation step arising from local temperature rising at the vial during high-energy milling that was understood from peak temperature, and area decrement of endothermic peak corresponds to decomposition of SrCO₃.     

A Novel Route to the Synthesis of Mesoporous Titania with Full Anatase Nanocrystalline Domains

A porous, high surface area TiO₂ with anatase or rutile crystalline domains is advantageous for high efficiency photonic devices. Here, we report a new route to the synthesis of mesoporous titania with full anatase crystalline domains. This route involves the preparation of anatase nanocrystalline seed suspensions as the titania precursor and a block copolymer surfactant, Pluronic P123 as the template for the hydrothermal self-assembly process. A large pore (7–8 nm) mesoporous titania with a high surface area of 106–150 m²/g after calcination at 400°C for 4 h in air is achieved. Increasing the hydrothermal temperature decreases the surface area and creates larger pores. Characteristics of the seed precursors as well as the resultant mesoporous titania powder were studied using XRD analysis, N₂-adsorption/desorption analysis, and TEM. We believe these materials will be especially useful for photoelectrochemical solar cell and photocatalysis applications.     

Estimation of the Thermodynamic Quality of Alkylbenzenes with Respect to Low Density Polyethylene

The original optical method was used for the first time to obtain complete diagrams of the state of mixtures of low-density polyethylene with o-xylene and ethylbenzene. The diagrams are of the type describing the phase state of systems partially crystalline polymer–good solvent. In contrast to the diagrams described in the literature, the diagrams described here contain an additional boundary curve for the solubility of the liquid in the polymer. Using the coordinates of the intersection of this line with the curve of complete amorphization of the polymer, five alkyl benzenes were ranked according to their thermodynamic affinity to low-density polyethylene.     

Synthesis and photoluminescence of titania nanoparticle arrays templated by block-copolymer thin films.

High-density arrays of titania nanoparticles were prepared using a polystyrene-b-poly(ethylene oxide) block copolymer (PS-b-PEO) as a template and a titanium tetraisopropoxide based sol-gel precursor as titania source via a spin-coating method. The hydrophilic titania sol-gel precursor was selectively incorporated into hydrophilic PEO domains of PS-b-PEO and form titania nanoparticle arrays, due to a microphase separation between the PS block and the sol-gel/PEO phase. Field emission scanning electron microscopy (FESEM) and scanning probe microscopy (SPM) images showed that the uniformity and long-range order of the titania/PEO domains improved with increasing sol-gel precursor amount. Grazing incidence small-angle X-ray scattering (GISAXS) results indicate that the ordered structures exist over large length scales. Titania nanocrystal arrays of anatase modification were obtained by calcination at 600 degrees C for 4 h. After calcination, separated particles were observed for low and medium amounts of sol-gel precursors. Films with higher precursor amounts showed wormlike structures due to the aggregation between neighboring particles. Removal of the polymer matrix via UV treatment leads to highly ordered arrays of amorphous titania while retaining the domain size and interparticle distance initially present in the hybrid films. Photoluminescence (PL) properties were investigated for samples before and after calcination. The PL intensity increases with the increasing amount of sol-gel precursor. Bands at 412 nm were ascribed to self-trapped exitons and bands at 461 and 502 nm to oxygen vacancies, respectively. Uncalcined or UV-treated samples also showed PL properties similar to calcined samples, indicating that the local environment of the titanium atoms is similar to the environment of the crystalline anatase modification.     

From Nanorods to Atomically Thin Wires of Anatase TiO2: Nonhydrolytic Synthesis and Characterization

A nonhydrolytic two‐step chemical process has been developed to synthesize ultrathin, nearly monodisperse TiO₂ (anatase) wires with tunable diameters of 5 nm to approximately 4 Å, reaching the atomic length scale. The high‐quality anatase titania atomically thin wires can be doped and stabilized with nitrogen species by introducing suitable nitrogen‐containing molecules. The ultrathin wires, particularly the atomically thin wires, as well as the precursor, have been thoroughly characterized by an extensive series of structural, spectroscopic, and other techniques. Possible formation mechanisms for the rods and the wires are proposed on the basis of experimental results obtained under varying reaction conditions. Also demonstrated are the pronounced effects of size and N‐doping on the electronic, optical, and phononic properties of the anatase titania wires in the smallest size regime.     

Application of synthesized mesoporous titania microspheres for arsenic [(III) and (V)] uptake studies

The present work describes the application of radiotracer technique for studying uptake of arsenic on titanium hydroxide, commercial titanium dioxide (TiO₂) powder (anatase) and synthesized mesoporous titania beads in acidic, neutral, and alkaline conditions. Sol–gel templating method was used to prepare titania–polysaccharide composites, with different polymer contents. Mesoporous titania was obtained by heat treatment of the composite beads in a controlled environment. The synthesis process was optimized, using thermogravimetry analysis. X-ray diffraction patterns confirmed the formation of anatase pure phase titania (TiO₂) at 700 °C in different environments, and scanning electron microscopy studies confirmed uniform pore size distribution. The effect of surface area, polymer content and pH on uptake of arsenic(III) and (V) on the synthesized titania beads was also investigated. Arsenic(V) was found to be retained quantitatively on the titania beads synthesized from 0.8% polymer content titania–polymer composite precursor in neutral to alkaline conditions. Details of the results obtained are discussed.     

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%.     

Spiky Mesoporous Anatase Titania Beads: A Metastable Ammonium Titanate‐Mediated Synthesis

A complex titania nanostructure of monodisperse spiky mesoporous anatase beads composed of anatase nanocrystals with diameters of less than 15 nm in the core and much larger hollow‐cone shaped spikes on the surface was fabricated using a facile solvothermal process in the presence of ammonia. This proceeded through a controllable phase transformation from an amorphous titania to a metastable amorphous titania/ammonium titanate core‐shell structure then finally to anatase titania. The size of the spiky anatase nanostructures can be increased from approximately 55×100 nm to 160×410 nm (square edge×length) by increasing the ammonia concentration used in the solvothermal treatment step from 2.2 to 17.4 wt. %. Such hollow‐cone shaped nanostructures, as revealed by HRTEM characterization, are single crystals elongated along the c axis of the tetragonal anatase titania. The resultant spiky titania beads have high surface areas of up to 112 m²g^?1 and pore diameters and pore volumes that vary depending on the ammonia concentration and solvothermal treatment time. The morphological evolution and crystallization process of the spiky titania beads was investigated using SEM and XRD techniques. A metastable amorphous titania/ammonium titanate core‐shell structure evolved from the smooth amorphous precursor beads producing a “fluffy” titanate intermediate, on further heating the final spiky mesoporous titania beads were clearly observed. This titanate‐phase‐mediated approach allows control over the size of the nanocrystals in the core of the bead, as well as the anatase spikes on the surface, and thereby, tuning of the surface area and porosity of the resultant products. The spiky mesoporous titania beads have been used to prepare working electrodes for dye‐sensitized solar cells achieving a solar to electric power conversion efficiency of 10.30 %, indicating their potential for application in the photovoltaic field. Such complex titania nanostructures would have a number of other possible applications, such as photocatalysis, lithium ion batteries, and catalysis.