The effects of the crystallization rate of the mesoporous TiO2 on the stability of the mesoporous structure after reflux

A simple synthetic method was employed to prepare mesoporous titania with anatase crystalline walls and high photocatalytic activity. The properties and structures of mesoporous titania were characterized by means of low angle and wide angle X-ray diffraction (XRD), Fourier transform (FT)-IR spectra, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and N₂ adsorption–desorption. The characteristic results clearly show that crystallization rate of the mesoporous titania affects the stability of the mesoporous structure after reflux, and that the anatase crystal in the mesoporous wall of mesoporous titania can stabilize the mesoporous structure. The photocatalytic activity of titania powder was evaluated from an analysis of the photodegradation of methyl orange under UV irradiation. The results indicate that the titania powder with mesoporous structure shows the highest photocatalytic activity.     

Application of tetrahydrofuran dispersant in microemulsion for fabricating titania mesoporous thin film

A new strategy was used to fabricate titania mesoporous thin film by incorporating tetrahydrofuran (THF) into the CTAB/n-butyl alcohol/cyclohexane/water reverse microemulsion as a micelle disperser. Highly dispersed and congregated TiO(2) particles in the microemulsion with and without THF were observed by transmission electron microscopy (TEM), respectively. The photographs observed by field-emission scanning electron microscopy (FE-SEM) show that a uniform titania mesoporous thin film with monodisperse TiO(2) spherical nanoparticles of ca. 20 nm was obtained using the microemulsion with THF.     

Visible light photocatalyst: iodine-doped mesoporous titania with a bicrystalline framework

Iodine-doped (I-doped) mesoporous titania with a bicrystalline (anatase and rutile) framework was synthesized by a two-step template hydrothermal synthesis route. I-doped titania with anatase structure was also synthesized without the use of a block copolymer as a template. The resultant titania samples were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared, nitrogen adsorption, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible absorption spectroscopy. Both I-doped titania samples, with and without template, show much better photocatalytic activity than commercial P25 titania in the photodegradation of methylene blue under the irradiation of visible light (>420 nm) and UV-visible light. Furthermore, I-doped mesoporous titania with a bicrystalline framework exhibits better activity than I-doped titania with anatase structure. The effect of rutile phase in titania on the adsorptive capacity of water and surface hydroxyl, and photocatalytic activity was investigated in detail. The excellent performance of I-doped mesoporous titania under both visible light and UV-visible light can be attributed to the combined effects of bicrystalline framework, high crystallinity, large surface area, mesoporous structure, and high visible light absorption induced by I-doping.     

硫和银共掺杂介孔TiO2的制备表征及光催化活性

以P123为模板,以钛酸四正丁酯、硝酸银和硫脲为原料采用模板法制备了一系列硫和银共掺杂介孔TiO2光催化材料。利用扫描电子显微镜（SEM）、X射线衍射（XRD）、BET和紫外-可见光谱（UV-Vis）等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征。以甲基橙溶液的光催化降解为模型反应, 考察了不同掺杂量的样品在紫外和可见光下的光催化性能。结果表明：用模板法制备的共掺杂介孔TiO2光催化材料在紫外和可见光条件下较纯介孔TiO2和单掺杂介孔TiO2对甲基橙溶液具有更好的光催化降解效果, 且硫和银的掺杂量及样品焙烧温度显著影响该材料的催化性能。当硫掺杂量为2%（mol）和银掺杂量为1%（mol）,在500℃焙烧2 h所得光催化材料的催化性能最佳, 4 h即可使甲基橙的降解率达98.8%,重复使用4次仍可使甲基橙的降解率保持在87.5%以上。因此, 以该模板合成法, 通过硫和银的共掺杂有望使TiO2成为一种低或无能耗、高活性的绿色环保型催化材料。     

Aerosol-assisted fabrication of mesoporous titania spheres with crystallized anatase structures and investigation of their photocatalitic properties

We demonstrate practical aerosol-assisted approach to synthesize spherical mesoporous titania particles with high surface areas. Scanning electron microscopy observation of the spray-dried products clearly shows spherical morphology. To remove surfactants and enhance crystallinity, the spray-dried products are calcined under various temperatures. The crystalline structures inside the particles are carefully detected by wide-angle XRD measurements. With increase of the calcination temperatures, anatase crystal growth proceeds and transformation from anatase to rutile is occurred. The effect of various calcination temperatures on the mesostructures is also studied by using N₂ adsorption desorption isotherms. The mesoporous titania particles calcined at 350, 400, and 500 °C exhibit type IV isotherms with a capillary condensation step and shows a hysteresis loop, which is a characteristic of mesoporous materials. The reduction in the surface areas and the pore volumes is confirmed by increasing the calcination temperatures, while the average pore diameters are increased gradually. This is attributed to the distortion of the mesostructures due to the grain growth of the anatase phase and the transformation to the rutile phase during the calcination process. As a preliminary experimental photocatalytic activity, oxidative decomposition of acetaldehyde under UV irradiation is examined. The mesoporous titania calcined at 400 °C shows the highest photocatalytic activity, due to both high surface area and well-developed anatase crystalline phase.     

Colloidal aspects relating to direct incorporation of TiO2 nanoparticles into mesoporous spheres by an aerosol-assisted process

Titania nanoparticles have been incorporated into spherical mesoporous silica powders by an aerosol-assisted synthesis process from both aqueous and ethanol-based precursor dispersions. Transmission electron microscopy (TEM) showed that the titania nanoparticles exist as single particles or small aggregates within the mesoporous carrier particles and analysis of the nitrogen adsorption isotherms proved that the pore blocking of the particles is small. Particle size and zeta potential measurements showed that the addition of tetraethoxysiloxane (TEOS), and also hexadecyl trimethyl ammonium bromide (C16TAB) induced flocculation of the TiO2 nanoparticles. The higher yield and narrower size distribution of the composite powder produced from ethanol-based dispersions compared to the aqueous dispersions could be related to a smaller degree of aggregation, indicated by rheological measurements.     

Photocatalytic activity of a hierarchically macro/mesoporous titania

Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules.     

锐钛矿型纳米TiO2介孔粉体表面织构的研究

以硫酸钛和尿素为原料,聚乙二醇-1000为空间构造剂,104℃下经尿素水解均匀沉淀法研制颗粒分散均匀、粒径可控的高热稳定性锐钛矿型纳米TiO2介孔粉体,并对其晶相、颗粒大小、比表面积、形貌和孔道结构进行了表征.结果表明,未经任何热处理的TiO2粉体即为锐钛型晶相,颗粒为均匀分散的类球型颗粒,且颗粒间形成直通型的介孔孔道,其孔径在10～30nm之间.控制焙烧温度可以达到控制颗粒大小及形貌的目的,经850℃焙烧5h的样品仍保持锐钛矿型晶相,未出现向金红石型晶相转变的迹象.     

Remarkable birefringence in a TiO2-SiO2 composite film with an aligned mesoporous structure

Mesoporous titania-silica composite films with highly aligned cylindrical pores are prepared by the sol-gel method using a substrate with structural anisotropy. The strong alignment effect of a rubbing-treated polyimide film on a substrate provides a narrow alignment distribution in the plane of the film regardless of the fast condensation rate of titania precursors. The collapse of the mesostructure upon the surfactant removal is effectively suppressed by the reinforcement of the pore walls with silica by exposing the as-deposited film to a vapor of a silicon alkoxide. The existence of a silica layer on the titania pore wall is proved from the distributions of Ti and Si estimated by the elemental analysis in high resolution electron microscopy. The obtained mesoporous titania-silica composite film exhibits a remarkable birefringence reflecting the highly anisotropic mesoporous structure and the high refractive index of titania that forms the pore wall. The Δn value estimated from the optical retardation and the film thickness is larger than 0.06, which cannot be achieved with the conventional mesoporous silica films with uniaxially aligned mesoporous structure even though the alignment of the pores in the films is perfect. These inorganic films with mesoscopic structural anisotropy will find many applications in the field of optics as phase plates with high thermal/chemical/mechanical stabilities.     

Formation and characterization of high surface area thermally stabilized titania/silica composite materials via hydrolysis of titanium(IV) tetra-isopropoxide in sols of spherical silica particles

A direct synthetic route leading to titania particles dispersed on nonporous spherical silica particles has been investigated; 5, 10, and 20% (w/w) titania/silica sols mixtures were achieved via hydrolyzation of titanium tetra-isopropxide solution in the mother liquor of a freshly prepared sol of spherical silica particles (St?ber particles). Titania/silica materials were produced by subsequent drying and calcination of the xerogels so obtained for 3 h at 400 and 600 degrees C. The materials were investigated by means of thermal analyses (TGA and DSC), FT-IR, N(2) gas adsorption-desorption, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). In spite of the low surface area (13.1 m(2)/g) of the pure spherical silica particles calcined at 400 degrees C, high surface area and mesoporous texture titania/silica materials were obtained (e.g., S(BET) ca. 293 m(2)/g for the 10% titania/silica calcined at 400 degrees C). Moreover, the materials were shown to be amorphous toward XRD up to 600 degrees C, while reasonable surface areas were preserved. It has been concluded that dispersion of titania particles onto the surface of the nonporous spherical silica particles increase their roughness, therefore leading to composite materials of less firm packing and mesoporosity.     

Synthesis and characterization of Nano titania particles embedded in mesoporous silica with both high photocatalytic activity and adsorption capability

TiO(2)-xSiO(2) composites with a high specific surface area (up to 645 m(2)/g), large pore volume, and narrow distribution with average pore sizes ranging from 15 to 20 A have been synthesized by the sol-gel method. The results of characterization by XRD, BET, TEM, FTIR, and DRUV reveal that these TiO(2)-xSiO(2) composites exhibit a core/shell structure of a nano titania/Ti-O-Si species modified titania embedded in mesoporous silica. As compared to pure anatase, the embedding of nano titania particles into the mesoporous silica matrix results in a substantial blue shift of absorption edge from 3.2 to 3.54 eV and higher UV absorption intensity, which are attributed to the formation of the Ti-O-Si species modified titania in the interface between titania and silica. The as-synthesized TiO(2)-xSiO(2) composites exhibit both much higher absorption capability of organic pollutants and better photocatalytic activity for the photooxidation of benzene than pure titania. The better photocatalytic activity of as-synthesized TiO(2)-xSiO(2) composites than pure titania is attributed to their high surface area, higher UV absorption intensity, and easy diffusion of absorbed pollutants on the absorption sites to photogenerated oxidizing radicals on the photoactive sites.     

Electron radiation damage of MCM-41 and related materials.

The article compares the relative stability of MCM-41 and related mesoporous materials in electron beam at an accelerating voltage of 100-300 kV. The work encountered in electron microscopy presents a comparison with similar research that has been carried out on nonporous and microporous silicates, especially alpha-quartz and zeolite Y. The trends in stability are analyzed, classifying the effects of sample preparation, organic and inorganic moieties, and electron accelerating voltage on beam stability. A higher synthesis temperature, the use of an acid catalyst in the synthesis, and the presence of additional organic or inorganic material within the channels were all found to stabilize these materials. The dose required to completely disrupt the structure increased with accelerating voltage for nearly all samples, suggesting a primarily radiolytic damage mechanism. The exception, MCM-41 containing nanometer-sized titania particles in its channels, was found to be almost insensitive to accelerating voltage.     

Thin Coatings with Photo-Catalytic Activity Based on Inorganic-Organic Hybrid Polymers Modified with Anatase Nanoparticles

Summary: Inorganic-organic hybrid polymer sols where modified with differently prepared as well as commercial titania nanoparticles, to obtain coatings exhibiting a photo-catalytic activity for the development of self-cleaning textiles. The particles synthesized using a sol-gel-approach where, amongst others, investigated by XRD to prove the existence of titania crystallized in the anatase structure. The photo-catalytic activity of the different particles as well of the coatings was compared by the decomposition of astrazone red induced by an irradiation with artificial and solar UV-radiation. With respect to the underlying aim of the investigation the durability of the effect against washing was tested by standardized washing experiments, showing promising results.     

Fabrication of size-tunable TiO2 tubes using rod-shaped calcite templates

Titania tubes with tunable wall thickness were produced by the sol-gel reaction of titanium(IV) n-butoxide in the presence of rod-shaped calcite particles that act as templates. A shell of amorphous titania was deposited around the calcite particles by sol-gel synthesis. The titania was crystallized to the anatase or rutile phase by sintering at different temperatures, and then acid etching was used to remove the calcite core, leaving hollow titania tubes. The influences of several parameters on the final particle formation were investigated, including calcite templates, surfactant, the method of adding reagents, and catalyst. The average width of the prepared titania tubes ranges from nearly 100 nm to 1 microm, with wall thickness ranging from approximately 70 to 300 nm. A possible growth mechanism of the titania tubes is presented. The ability to control titania tube size and crystal structure is important for photocatalysis, photovoltaics, and other applications. The fabrication approach presented is applicable to form tubes of other oxide materials by sol-gel synthesis.     

Effect of an anionic monomer on the pickering emulsion polymerization stabilized by titania hydrosol

Polystyrene (PS) nanocomposite particles with high titania content are prepared by Pickering emulsion polymerization. A self‐made titania hydrosol modified by an anionic monomer sodium styrene sulfonate (NaSS) is used as a stabilizer and photocatalyst. The stability of the emulsion system is greatly improved by the electrostatic interaction between negatively charged NaSS and positively charged titania nanoparticles. The nanocomposite spheres with the diameter of around 120 nm are highly charged, indicating titania‐rich surfaces of latex particles. It is also proven by the field‐emission transmission electron microscope and field‐emission scanning electron microscope images. The well‐defined core‐shell structure of the obtained PS/titania composite particles is confirmed by the formation of fragile hollow titania nanospheres after thermogravimetric analysis tests. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5728–5736, 2009     

Photocatalytic activity of structured mesoporous TiO2 materials

Starting from colloidal TiO2 nanoparticles in combination with tetraethyl orthosilicate using neutral Pluronic or cationic cetyltrimethylammonium as templates, a series of structured mesoporous silicas has been obtained. The structure of the mesoporous titania was confirmed by isothermal gas adsorption, transmission electron microscopy, and X-ray diffraction. The pore diameter ranged between 3.8 and 10.9 nm, and the BET surface area varied from 99 to 584 m2 g(-1). The photocatalytic activity of these samples for the degradation of phenol in aqueous solution has been compared with that of standard P-25 TiO2. Even though the activity of these new mesostructured materials is lower that those found for P-25 TiO2, the turnover frequency of the photocatalytic activity (moles of phenol degraded per Ti atom present at initial reaction time) is much higher for the mesoporous titania, particularly with low titanium contents for those materials (mpTiO2-5 and TiO2SBA15-5).     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

含 TiO2(B) 介孔氧化钛材料的制备、特性和应用

 综述了近年来本课题组依据材料化学工程研究思想, 对含 TiO2(B)(一种比金红石和锐钛矿相结构更松散的氧化钛晶型) 介孔氧化钛材料在制备、结构和性能方面所取得的研究进展. 该介孔材料由二钛酸钾经水合、离子交换和热处理得到, 具有良好原子尺度晶格匹配界面特征的锐钛矿和 TiO2(B) 核壳结构. 研究表明, 该介孔材料在兼备高比表面积、高晶化孔壁和高热稳定性的同时, 还表现出良好的纳米颗粒担载稳定性, 在光催化、油品加氢精制、药物载体、固体酸催化和电化学电容器等方面已凸显出良好的应用潜力和推广价值. 目前该新型含 TiO2(B) 介孔氧化钛材料已经实现低成本、规模化制备.     

新型晶须状氧化钛担载Au的CO催化氧化性能

从钛钾比较高的二钛酸钾晶须出发,通过离子交换和热处理等步骤制备了具有不同微观结构的晶须状TiO2,然后通过均相沉积-沉淀法在制得的TiO2上担载1%的Au.采用X射线衍射、扫描电镜、低温N2吸附-脱附及透射电镜等技术对催化剂样品进行了表征,并测定了其催化CO氧化反应性能.结果表明,600℃处理所得晶须状TiO2载体(T(600))具有丰富的介孔结构,比表面积为59 m2/g,平均孔径为11 nm,担载Au后其孔道结构保持良好,而800℃处理所得晶须状TiO2样品(T(800))孔结构完全坍塌,但仍保持纯锐钛矿晶型.在相同担载条件下Au/T(800)上的Au颗粒尺寸明显小于Au/T(600)上的,但两者催化CO氧化反应活性相差不大,CO完全转化温度分别为80和70℃,活性均比Au/P25的高.     

Gold Nanoparticles Supported on Mesoporous Titania Thin Films with High Loading as a CO Oxidation Catalyst

In the present work, 2.4 nm gold nanoparticles (Au NPs) are uniformly dispersed on mesoporous titania thin films which are structurally tuned by controlling the calcination temperature. The gold content of the catalyst is as high as 27.8 wt %. To our knowledge, such a high loading of Au NPs with good dispersity has not been reported until now. Furthermore, the reaction rate of the gold particles is enhanced by one order of magnitude when supported on mesoporous titania compared to non‐porous titania. This significant improvement can be explained by an increase in the diffusivity of the substrate due to the presence of mesopores, the resistance to agglomeration, and improved oxygen activation.