One-pot synthesis of highly crystalline mesoporous TiO2 nanoparticle assemblies with enhanced photocatalytic activity

We report an unprecedented formation of mesoporous titania via a surfactant-assisted aggregating assembly of TiO(2) nanoparticles. These mesostructures possess a highly crystalline anatase phase, large and accessible pore surface area, and exhibit superior photocatalytic performance.     

Preparation and photocatalytic activity of multi-modally macro/mesoporous titania

Hierarchically disorder sponge-like macro/mesoporous titania was prepared by adding distilled water dropwise to a coating of tetrabutyl titanate. The results reveal that the un-calcined samples show obvious photocatalytic activity and multi-modal pore-size distribution. With increasing calcination temperatures, the photocatalytic activity and crystallinity increase. At 400°C, the calcined sample shows the highest photocatalytic activity. Further increasing the calcination temperatures results in the decrease of photocatalytic activity due to the drastic decrease of specific surface areas. However, the 600°C-calcined sample exhibits the highest specific photocatalytic activity due to high anatase crystallinity.     

The effect of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders

Mesoporous F⁻-doped TiO₂ powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in a mixed NH₄F-H₂O solution. Effects of F⁻ ion content and calcination temperatures on the phase composition and porosity of mesoporous titania were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and BET surface areas. The results showed the BET surface area (S_BET) of the pure and doped powders dried at 100°C ranged from 260 to 310 m²/g as determined by nitrogen adsorption. With increasing calcination temperatures, the S_BET values of the calcined titania powders decreased due to the increase in crystalline size. The pore size distribution was bimodal with fine intra-particle pore and larger inter-particle pore as determined by nitrogen adsorption isotherms. The peak pore diameter of intra-particle pore increases with increasing F⁻ ion content. At 700°C, all the titania powders exhibit monomodal pore size distributions due to the complete collapse of the intra-particle pores. The crystallization of anatase was obviously enhanced due to F⁻-doping at 400°C and 500°C. Moreover, with increasing F⁻ ion concent, F⁻ ions not only suppressed the formation of brookite phase at low temperature, but also prevented phase transition of anatase to rutile at high temperature.     

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.     

Enhanced photoactivity of neodymium doped mesoporous titania synthesized through aqueous sol–gel method

Nanosize neodymium doped titania has been prepared by hydrolysis of titanium oxychloride followed by peptisation under acidic condition. The anatase to rutile phase transformation temperature was found to increase by 150 °C as a result of neodymium doping. The doped sample shows 10 times higher surface area than the undoped one after calcining at 700 °C. All the samples calcined at 500, 600 and 700 °C show type IV isotherm, which is characteristic of mesoporous material. The pore size distribution curves also show that the pores are in mesoporous region. Further, the neodymium doped titania shows increased photoactivity than the undoped titania with respect to decomposition of methylene blue when subjected to UV light. The transmission electron micrograph indicates that a nanocrystalline doped titania is obtained through the present method. The effect of neodymium doping on the anatase phase stability, specific surface area and photoactivity are reported.     

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.     

Synthesis, characterization, and photocatalytic activity for hydrogen evolution of nanocrystalline mesoporous titania prepared by surfactant-assisted templating sol-gel process

Nanocrystalline mesoporous titania was synthesized via a combined sol-gel process with surfactant-assisted templating method, treated under various calcination conditions, and evaluated for its photocatalytic activity through photocatalytic hydrogen evolution from an aqueous methanol solution. In this synthetic method, applied surfactant template molecules functioned as both mesopore-forming and gelation-assisting agents. The resulting products were methodically characterized by TG-DTA, XRD, N₂ adsorption-desorption, diffuse reflectance UV-Vis spectra, SEM, and TEM analyses. The partial phase transformation from anatase to rutile occurred beyond calcination temperature of 600 °C and anatase-rutile transition kinetics was also investigated. The calcination conditions and crystalline phases existing in the products exerted significant effect on the photocatalytic hydrogen evolution activity. The activity of the synthesized titania treated under appropriate calcination conditions was considerably higher than that of commercial titania powders, Ishihara ST-01 and Degussa P-25. It is clearly seen that the introduction of mesopore into titania photocatalyst substantially improved the photocatalytic performance.     

UV Raman spectroscopic study on TiO2. I. Phase transformation at the surface and in the bulk

Phase transformation of TiO2 from anatase to rutile is studied by UV Raman spectroscopy excited by 325 and 244 nm lasers, visible Raman spectroscopy excited by 532 nm laser, X-ray diffraction (XRD), and transmission electron microscopy (TEM). UV Raman spectroscopy is found to be more sensitive to the surface region of TiO2 than visible Raman spectroscopy and XRD because TiO2 strongly absorbs UV light. The anatase phase is detected by UV Raman spectroscopy for the sample calcined at higher temperatures than when it is detected by visible Raman spectroscopy and XRD. The inconsistency in the results from the above three techniques suggests that the anatase phase of TiO2 at the surface region can remain at relatively higher calcination temperatures than that in the bulk during the phase transformation. The TEM results show that small particles agglomerate into big particles when the TiO2 sample is calcined at elevated temperatures and the agglomeration of the TiO2 particles is along with the phase transformation from anatase to rutile. It is suggested that the rutile phase starts to form at the interfaces between the anatase particles in the agglomerated TiO2 particles; namely, the anatase phase in the inner region of the agglomerated TiO2 particles turns out to change into the rutile phase more easily than that in the outer surface region of the agglomerated TiO2 particles. When the anatase particles of TiO2 are covered with highly dispersed La2O3, the phase transformation in both the bulk and surface regions is significantly retarded, owing to avoiding direct contact of the anatase particles and occupying the surface defect sites of the anatase particles by La2O3.     

Photocatalytic Degradation of Acetaldehyde on Mesoporous TiO2: E?ects of Surface Area and Crystallinity on the Photocatalytic Activity

"Mesoporous TiO2 powder and films with worm-like channels were synthesized by an evaporation-induced self-assembly approach. The as-prepared samples were calcined at different temperature to investigate the effect of calcined temperature on the mesostructure and the photocatalytic activity. Acetaldehyde photodegradation in gas phase was employed to evaluate the photocatalytic activity of mesoporous TiO2. Results showed that all the calcined powder samples exhibited higher photocatalytic activities than that of Degussa P25. The sample calcined at 400 oC, which showed higher activity than other samples, possessed a homogeneous pore diameter of about 6.0 nm and an 11.0 nm crystalline anatase pore wall, as well as large surface area of 117 m2/g. It was speculated that two factors of surface area and crystallinity affected the photocatalytic activity of mesoporous TiO2 photocatalyst. The mesoporous TiO2 films fabricated by spin-coating also had high photocatalytic activities."     

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.     

Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Photoluminescence and photoactivity of titania particles prepared by the sol–gel technique: effect of calcination temperature

The photoluminescence (PL) characteristics of anatase titania particles prepared by the sol–gel method were investigated and correlated to their photocatalytic behavior with respect to the change of calcination temperature. It was found that the photoluminescence intensity measured at 77 K was gradually increased by increasing the calcination temperature due to the reduction of the internal defects which are responsible for the radiationless recombination of photoexcited electron/hole pairs. Also, the calcination temperature was found to influence the maximum peak position (λ) of the photoluminescence spectra of titania. That is, a blue shift of the photoluminescence spectrum occurs as a consequence of the enlargement of the energy-gap between the lowest excited state and the ground state of titania as increasing the calcination temperature. The quenching behavior of the photoluminescence at 77 K was monitored by in situ supplying oxygen at 77 K in order to investigate what happened to the surface of titania by the calcination. The quenching intensity was monotonically increased with increasing the calcinations temperature. Based on the above results, we concluded that the calcination of titania at higher temperature produces more surface-active sites easily reacting with oxygen molecules as well as improving the crystallinity of anatase phase. Consequently, higher temperature heat treatment of anatase titania particles makes it possible to get higher photoactivity as long as no significant rutile phase is formed.     

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.     

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.     

Synthesis and Characterization of Microporous Titania Membranes

A procedure for the preparation of microporous titania membranes by the polymeric sol-gel technique is reported. The influence of acid/titanium ratio, water/titanium ratio, method of mixing components and refluxing time on particle size and sol stability was investigated. The thermal evolution, structural characteristics and liquid permeation properties of calcined materials were studied. Highly reproducible amorphous microporous titania layers with pore sizes ≤0.8 nm were obtained on both mesoporous γ-alumina and titania/zirconia coated substrates. The upper limit of thermal stability of the amorphous phase is ～300°C. Higher calcination temperatures led to phase transformation into anatase, which was accompanied by a collapse of the microstructure. The material was found to be chemically stable in a wide pH interval.     

Surfactant mediated synthesis of spherical binary oxides photocatalytic with enhanced activity in visible light

Spherical silica and zirconia mixed titania and pure titania samples were prepared in presence of cetyltrimethylammonium bromide (CTAB) through controlled hydrolysis of corresponding metal alcoxides. Effect of surfactant amount and calcinations temperature on morphology, surface area and photocatalytic activity is studied using PXRD, SEM, FTIR, Solid state UV-vis spectroscopy and BET surface area. It is well observed that in presence of 2 mol% CTAB, uniform sized spherical oxide particles can be synthesized. However, increasing or decreasing the surfactant amount does not favor the spherical particle formation. Material synthesis in presence of CTAB not only helps in the spherical particle formation but also increases the surface area and visible light absorption. Studies on photocatalytic lead removal with respect to calcination temperature indicate that the calcination at 500 degrees C is most suitable for the best photocatalytic activity. Mixing of zirconia and silica helps in anatase phase stabilization even at 900 degrees C calcination. Accordingly low decrease in surface area even at 900 degrees C calcination is observed. Due to the phase stabilization and higher surface area binary oxide materials showed comparatively better photocatalytic activity even after calcination at 900 degrees C. So it can be concluded that present synthesis approach can produce uniform sized spherical binary oxide materials with better photocatalytic activity in visible light.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Preparation and characterization of SiO2/TiO2 composite microspheres with microporous SiO2 core/mesoporous TiO2 shell

SiO₂/TiO₂ composite microspheres with microporous SiO₂ core/mesoporous TiO₂ shell structures were prepared by hydrolysis of titanium tetrabutylorthotitanate (TTBT) in the presence of microporous silica microspheres using hydroxypropyl cellulose (HPC) as a surface esterification agent and porous template, and then dried and calcined at different temperatures. The as-prepared products were characterized with differential thermal analysis and thermogravimetric (DTA/TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption. The results showed that composite particles were about 1.8 μm in diameter, and had a spherical morphology and a narrow size distribution. Uniform mesoporous titania coatings on the surfaces of microporous silica microspheres could be obtained by adjusting the HPC concentration to an optimal concentration of about 3.2 mmol L⁻¹. The anatase and rutile phase in the SiO₂/TiO₂ composite microspheres began to form at 700 and 900 °C, respectively. At 700 °C, the specific surface area and pore volume of the SiO₂/TiO₂ composite microspheres were 552 and 0.652 mL g⁻¹, respectively. However, at 900 °C, the specific surface area and pore volume significantly decreased due to the phase transformation from anatase to rutile.     

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.     

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.