工业硫酸氧钛合成有序介孔TiO2及其机理研究

采用复合表面活性剂CTAB和P123形成的超分子模板为结构导向剂,以工业硫酸氧钛液为钛源,控制溶液pH值及水解条件调控TiOSO₄的水解缩聚及与模板剂的自组装速率,钛水解胶粒通过界面作用形成介孔前驱体,脱模后制得二维六方,比表面积为205.7m²/g,平均孔径为3.28nm的锐钛型有序介孔TiO2. 用XRD、HRTEM、SAED及等温N2吸附等对样品进行了表征,初步探讨了介孔的形成过程. 钛水解胶粒和复合模板剂通过界面处的静电和氢键等相互作用,协同形成介孔结构,属协同作用机理.     

Pt/介孔TiO2-SiO2的制备、表征及光催化性能研究

以正硅酸乙酯、钛酸异丙酯为前驱体，尿素为沉淀剂，改进的均匀沉淀法制备了TiO2-SiO2介孔复合材料，用XRD、FTIR、氮气吸附-脱附、XPS等对材料进行了表征．结果表明：Ti／Si摩尔比为0．5的介孔复合材料平均孔径为3．2nm，比表面积达到609m^2／g．用光还原法在材料表面沉积适量的贵金属Pt，大大提高了材料的光催化活性．     

Preparation of TiO2/Al-MCM-41 mesoporous materials from coal-series kaolin and photodegradation of methyl orange

TiO₂/Al-MCM-41 mesoporous materials were prepared via sol-gel method by loading titania onto Al-MCM-41 mesoporous molecular sieve by hydrothermal treatment from coal-series kaolin as raw material. The TiO₂/Al-MCM-41 mesoporous materials were characterized by XRD, FT-IR, HRTEM, N₂ adsorption-desorption and the photocatalytic degradation of methyl orange solution under visible light irradiation. The results showed that the TiO₂/Al-MCM-41 mesoporous materials possessed a high surface area of 369.9–751.3 m²/g and a homogeneous pore diameters of 2.3–2.8 nm. The titania crystalline phase was anatase, and the particles size of TiO₂ increased with TiO₂ content. The Al-MCM-41 mesoporous materials exhibited excellent photodegradation activity under visible-light irradiation for methyl orange.     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

介孔氧化钛晶须的合成及机理研究

利用二钛酸钾(K₂Ti₂O₅)独特的三角双锥层状晶体结构, 通过水化反应过程, 控制其介相结构转变, 获得介孔氧化钛晶须, 经N₂吸附-脱附测试比表面积为248m²/g. 高温500℃晶化为锐钛矿型, 比表面积仍可达139m²/g, 孔径为8.7nm, 并且晶须形貌不变. 通过XRD、TEM和HREM等手段, 考察了水化反应过程中K₂Ti₂O₅的结构变化, 提出KOH·nH₂O纳米相的形成是介孔结构的来源.     

模板法制备介孔TiO2及其光催化性能研究

以十六烷基三甲基溴化铵(CTAB)作为模板剂,钛酸正四丁酯(TBOT)为钛源,异丙醇为溶剂,通过溶胶-凝胶过程合成出介孔TiO2前驱体凝胶后,经老化、焙烧得到了TiO2介孔材料.利用XRD、HR-TEM、TGA、N2的吸附-脱附、BET等方法对材料的结构、形貌、比表面积、孔径分布进行表征.以亚甲基蓝的降解为模型反应,对其催化性能进行评价并与商品DegussaP-25进行比较.实验结果表明,比表面积为137.5m2/g、孔径为8.62nm的锐钛型介孔TiO2具有很高的催化活性.     

Poly(methyl methacrylate)–titania hybrid materials by sol–gel processing

Sol–gel derived poly(methyl methacrylate)–titania hybrid materials were synthesized by using acrylic acid or allyl acetylacetone (3-allyl-2,4-pentanedione) as coupling agent. Titanium butoxide modified with acrylic acid (or titanium isopropoxide modified with allyl acetylacetone) was hydrolysed to produce a titania network, and then poly(methyl methacrylate) (PMMA) chains, formed in situ through a radical polymerization, were chemically bonded to the forming titania network to synthesize a hybrid material. Transparent hybrid materials with different contents of titania were achieved. With increase of the titania content, the colours of the products changed from yellow to dark red. The synthesis process was investigated step by step by using Fourier transform–infrared spectroscopy, and the experimental results demonstrated that acrylate or acetylacetonato groups bound to titanium remain in the final hybrid materials. The thermal stability of the hybrid materials was considerably improved relative to pure PMMA. Field emission scanning electron microscopy analyses showed the hybrid materials are porous and pore diameters vary from 10–100 nm. The hybrid materials using allyl acetylacetone as coupling agent exhibited a thermochromic effect that neither pure PMMA nor titania exhibit. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of Microstructure on Electrorheological Property for Pure TiO2 Particle Material

Pure titanium dioxide （TiO2） particle materials were prepared by hydrolyzing titanium tetrachloride （TiCl4）. The microstructures of these materials were determined by X-ray diffraction （XRD）, accelerated surface area and porosimetry apparatus （BET）, and transmission electron microscopy （TEM）. The TiO2 materials obtained by calcinations under different temperatures distinctly revealed different microstructures in crystal structure type, surface area, pore size, pore volume and grain size. The relationship between the microstructure of the TiO2 materials and their electrorheological （ER） activity was investigated. Anatase titania particles have better ER performance than rutile titania particles. Amorphous TiO2 materials display higher ER activity than the crystalline titania materials. A large pore volume can be more advantageous in improving the ER effect of a particle material.     

Effect of Microstructure on Electrorheological Property for Pure Particle Material

Pure titanium dioxide (TiO2) particle materials were prepared by hydrolyzing titanium tetrachloride (TiCl4). The microstructures of these materials were determined by X-ray diffraction (XRD), accelerated surface area and porosimetry apparatus (BET), and transmission electron microscopy (TEM). The TiO2 materials obtained by calcinations under different temperatures distinctly revealed different microstructures in crystal structure type, surface area, pore size, pore volume and grain size. The relationship between the microstructure of the TiO2 materials and their electrorheological (ER) activity was investigated. Anatase titania particles have better ER performance than rutile titania particles. Amorphous TiO2 materials display higher ER activity than the crystalline titania materials. A large pore volume can be more advantageous in improving the ER effect of a particle material.     

醇热法制备介孔TiO2及其光催化性能

以十六烷基三甲基溴化铵(CTAB)为模板剂,钛酸正四丁酯(TBOT)为钛源,异丙醇为溶剂,通过醇热法合成介孔TiO_2,用N_2吸附-脱附、XRD、TEM等技术对合成样品进行了表征。以亚甲基蓝的降解为模型反应,对介孔TiO_2催化性能进行评价并与商品DegussaP-25比较。实验结果表明,比表面积为248.8 m~2·g~(-1),孔径为4.92 nm的锐钛矿晶型介孔TiO_2具有很高的催化活性。     

结构有序、双重孔隙中孔炭材料的合成与表征

采用纳米涂层技术,以介孔分子筛SBA 15为模板,在其纳米孔道内引入糠醇/草酸溶液,经原位聚合,炭化后制得炭/SBA 15复合物。采用化学法脱除模板后制得具有规则结构的中孔炭。高分辨TEM表征结果显示该中孔炭是由纳米炭管相互联接、堆积而成,且具有六方对称结构。氮吸附结果显示其比表面积高达2000m2/g,孔径呈双峰分布。孔径相对较大的孔隙来源于SBA 15孔道经纳米涂层后所保留的孔隙;孔径相对较小的孔隙来源于SiO2移除后遗留的纳米孔空间。该方法可应用于以其他多孔氧化硅为模板制备新型纳米复合物的研究过程。     

酸对合成二氧化钛介孔材料的影响

以硫酸和乙酸为酸度调节试剂,采用Sol-Gel过程和水热处理结合,在没有添加任何表面活性剂作模板剂的条件下,通过钛酸丁酯（TBOT）在酸性体系中的控制水解和自组装制备TiO₂介孔材料.产物采用XRD、N₂吸附-脱附等温线、TG-DSC进行分析表征.通过选择酸的种类和控制酸的浓度,添加配位抑制剂TEA减缓Ti的水解速率,可合成介孔纯TiO₂材料.使用硫酸（H₂SO₄∶TBOT＝1∶1,摩尔比）和TEA制备出比表面积为176m²/g,孔容为0.222cm³/g,平均孔径约5nm,孔径分布窄,热稳定性较好的TiO₂介孔材料.     

Vapor-phase photo-oxidation of methanol over nanosize titanium dioxide clusters dispersed in MCM-41 host material part 1: synthesis and characterization

Nanosize clusters of titania were dispersed in mesoporous MCM-41 silica matrix with the help of the incipient wet-impregnation route, using an isopropanol solution of titanium isopropoxide as precursor. The clusters thus formed were of pure anatase phase and their size depended upon the titania loading. In the case of low (< 15 wt %) loadings, the TiO2 particles were X-ray and laser-Raman amorphous, confirming very high dispersion. These particles were mostly of < or = 2 nm size. On the other hand, larger size clusters (2-15 nm) were present in a sample with a higher loading of approximately 21 wt %. These particles of titania, irrespective of their size, exhibited an absorbance behavior similar to that of bulk TiO2. Powder X-ray diffraction, N2-adsorption and transmission electron microscopy results showed that while smaller size particles were confined mostly inside the pore system, the larger size particles occupied the external surface of the host matrix. At the same time, the structural integrity of the host was maintained even though some deformation in the pore system was noticed in the case of the sample having highest loading. The core level X-ray photoelectron spectroscopy results revealed a + 4 valence state of Ti in all the samples. A positive binding energy shift and the increase of the width of Ti 2p peaks were observed, however, with the decrease in the particle size of supported titania crystallites, indicative of a microenvironment for surface sites that is different from that of the bulk.     

One-pot synthesis of supported-nanoparticle materials in ionic liquid solvents

Highly porous supported-nanoparticle materials were synthesized by a rational method involving the encapsulation of poly(vinylpyrrolidone) (PVP)-stabilized Au nanoparticles into titania xerogels employing room temperature ionic liquids (1-butyl-3-methylimidazolium hexaflurophosphate, [BMIM]PF₆) as a medium followed by solvent extraction of the ionic liquid and calcination of the materials. The materials were thoroughly characterized by TEM, nitrogen adsorption-desorption isotherms, and XRD. After calcinations at 350 °C, the Au-titania system resulted in the formation of a highly mesoporous materials with BET surface areas of 200 m²/g and average pore sizes of 3-5 nm. These materials can find potential applications in catalysis and photocatalysis.     

Photocatalytic properties of the SBA-15 mesoporous silica molecular sieve modified with titanium

We describe three methods of post-synthesis modification of the SBA-15 mesoporous molecular sieve with titanium: impregnation with Ti(OEt)₄ in an ethanolic solution, grafting with titanocene dichloride, and modification with colloidal titania. The products were characterized using X-ray diffraction (XRD) and N₂ adsorption as well as Fourier-transform infrared and ²⁹Si NMR spectroscopies. All three methods yield materials containing 1.4--4.7 wt.% titanium and with high surface areas. The absorbance at 960 cm⁻¹ in SBA-15 modified with colloidal titania and SBA-15 grafted with titanocene indicates the formation of Ti–O bonds. All products showed significant activity towards the degradation of p-chlorophenol. UV-vis absorption spectra of SBA-15 samples modified with titanium indicate that the variation in the photocatalytic activity is governed by isolated titanium sites.     

Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

Abstract

This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.     

Synthesis and characterization of ordered and cubic mesoporous silica crystals under a moderately acidic condition

Ordered and cubic mesoporous silica materials were synthesized by using poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer as template under a moderately acidic condition of 0.5 mol/l HCl solution. These mesoporous materials were characterized by Fourier transform (FT) IR spectroscopy, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption–desorption measurements. The three-dimensional cage-like microporosity of the prepared mesoporous silica having ordered hexagonal mesoporous structure was evidenced by the well-defined XRD patterns combined with TEM photographs. SEM observation shows a highly regular cubic crystal structure for the prepared mesoporous silica. The size of these crystallites was maintained within the range between 4 and 6 μm, which is fairly important for the application to the stationary phase for separation. The nitrogen adsorption–desorption analysis reveals that the prepared mesoporous silica possesses a small pore diameter of 3.68 nm, a total surface area of 363.648 m²/g, a total pore volume of 0.379 cm³/g, and a pore-wall thickness of 6.63 nm. These features may lead to higher thermal and hydrothermal stability, excellent microporosity, and good connectivity. The mesoporous silica prepared in this study exhibits potential applications to catalysis, sensoring, and separation.     

Synthesis, characterization and photocatalytic activity of mesoporous titania nanorod/titanate nanotube composites

Mesoporous titania nanorod/titanate nanotube composites were prepared using TiF4 and H(3)BO(3) as the precursors. The prepared samples were characterized with TEM, SEM, XRD, HRTEM, and nitrogen adsorption-desorption isotherms. The photocatalytic activities were evaluated by photocatalytic oxidation of acetone in a gas phase and photocatalytic discolorization of methyl orange aqueous solution in an aqueous phase, respectively. The results indicated that the photocatalytic activity of the mesoporous titania nanorod/titanate nanotube composites exceeded that of P25 by a factor of about 2.5 times for the photocatalytic oxidation of acetone. This could be attributed to the fact that the former had a larger specific surface area and a higher pore volume. Moreover, the mesoporous titania nanorod/titanate nanotube composites, which could be readily separated after photocatalytic reaction in an aqueous phase, exhibited highly photocatalytic activity for the degradation of methyl orange aqueous solution.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

活化凹凸棒石合成多级孔钛硅分子筛及其光催化性能研究EI北大核心CSCD

以天然凹凸棒石为硅源,钛酸丁酯为钛源,四丙基氢氧化铵为模板剂一步水热合成钛硅分子筛,并研究了钛硅比对合成产物结构和性能的影响。通过XRD,SEM,UV-Vis和N_(2)吸附-脱附对钛硅分子筛的晶体结构、形貌、钛的存在形式和孔道特征进行表征,并对亚甲基蓝印染废水进行光催化实验考察分子筛的光催化性能。结果表明,当钛硅比为1∶30时,其XRD特征峰强,结晶度高,晶粒大小均匀,呈规则六棱柱状,钛以骨架钛和锐钛矿型TiO_(2)形式存在,孔道结构兼具微孔和介孔。分子筛具有光催化性,光催化反应遵循拟一级反应动力学。利用响应曲面法建立模型优化pH=7.8亚甲基蓝溶液最佳实验条件为初始浓度10.0 g/mL,光催化时间48 min,投加量0.05 g,经光催化降解溶液脱色率达到98.75%。