Controllable preparation of nanosized TiO<Subscript>2</Subscript> thin film and relationship between structure of film and its photocatalytic activity

TiO₂ nano-crystalline film and fixed bed photocatalytic reactor were prepared by the sol-gel process using tetrabutylorthotitanate as a precursor and glass tube as the substrate. XRD, AFM, SEM and thickness analysis results indicate that the preparation of nano-crystalline film can be controlled by optimizing experiment process. Under the optimized process, the phase of TiO₂ in film is anatase, and the grain size is 3–4 nm. The size of particles, which is about 20-80 nm, can be controlled. The thickness of monolayer film is in nanometer grade. The thickness and particles size in films growing on nanometer film can also be controlled in nanometer grade. As a result, the crack of film can be effectively avoided. Rhodamine degradation results using UV-Vis spectrophotometer show that the activity of nano-crystalline film in the photocatalytic reactor has a good relation with the diameter of TiO₂ particles, that is, the film shows high activity when the size is 20 –30 nm and greatly reduced when the size is above 60 nm. The activity of film does not decrease with the increase of film thickness, and this result indicates that nano-crystalline film has no ill influence on the transmissivity of ultraviolet light.     

铝基板的界面扩散对薄膜型TiO2光催化活性的影响

以钛酸四丁酯为前驱体, 采用溶胶-凝胶法在铝基板表面制备了纳米晶TiO2薄膜. 运用XRD、SEM和XPS对制得的薄膜进行表征, 并测试了薄膜光催化降解亚甲基蓝(MB)的活性. 结果表明, TiO2薄膜样品在450 ℃焙烧30 min后, 晶粒排列比较致密, 粒径为10-20 nm, 并与铝基板紧密结合; 薄膜与铝基板发生了明显的界面扩散, 薄膜中的Al元素来自铝基板的界面扩散, 且界面层很宽, 扩散层厚度约为75 nm; 界面扩散的发生直接导致了TiO2薄膜的光催化活性下降. 但随着薄膜厚度增加, 铝基板对TiO2薄膜降解亚甲基蓝催化活性的影响不断减小.     

微乳法制备纳米TiO2 /SiO2的结构及光催化研究

Nanosized TiO₂ and TiO₂/SiO₂ particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM，N₂ adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO₂/SiO₂ nanoparticles are with a monodispersed spherical phase and a uniform size distribution，and TiO₂ particles are dispersed on the surface of SiO₂. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO₂, suppressed the phase transformation of titania from anatase to rutile. And due to the addition of SiO₂, the average size of titania decreased from 38 nm in pure TiO₂ to 5 nm in TiO₂/SiO₂. It was found, under UV light irradiation, TiO₂/SiO₂ particles showed higher activity than pure TiO₂, and TiO₂/SiO₂(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.     

TiO_2/SiO_2纳米薄膜的光催化活性和亲水性

通过 sol-gel工艺在钠钙玻璃表面制备了均匀透明的 TiO2/SiO2复合纳米薄膜 .实验结果表明 : 当 SiO2添加量较高时 , TiO2/SiO2复合纳米薄膜的光催化活性明显降低 ;当 SiO2添加量较低时 ,TiO2/SiO2复合薄膜的光催化活性无明显变化 .在 TiO2薄膜中添加 SiO2,可以抑制薄膜中 TiO2晶粒的长大 ,同时薄膜表面的羟基含量增加 , 水在复合薄膜表面的润湿角下降 , 亲水能力增强 .当 SiO2含量为 10％－ 20％（摩尔分数）时获得了润湿角为 0°的超亲水性薄膜 .     

Supported nanometric titanium oxide sols as a new efficient photocatalyst

We report on the first study of the photocatalytic performance of immobilized smallest titanium oxide oxoparticles of the size 2R = 5.0 nm on a glass support. The nanometric particles are prepared in the sol-gel reactor with rapid reagent mixing and temperature, atmosphere, and particle size control. The surface coverage is achieved by inserting the support into the reactor solution during the induction period, where chemically active nanoparticles are relatively stable. We show that this immobilized amorphous oxo phase of titanium oxide exhibits considerable activity toward photocatalytic degradation of trichloroethylene in the gas phase. Moreover, one of the important factors appears to be the catalyst surface preparation, which has to be free of the adsorbed alcohol molecules. UV-assisted exchange between propoxy and hydroxy groups is suggested as the surface activation mechanism. The film thickness is expected to strongly affect the material photocatalytic efficiency because of the internal traps population.     

PREPARATION OF NANOMETER TiO2 ORGANIC SOLUTION-EFFECT OF ORGANIC SILOXANE ON SOL PROPERTIES

A homogeneous longtime stabilized transparent nanometer TiO2 organic solution was obtained by means of the simultaneous hydrolysis and co-polycodensation of tetrabutyltitanate (TBT) and methacryloxypropyltrimethoxysilane (MAPTMS) by the sol-gel process. The particle size of nanometer titanium dioxide was controlled by use of bifunctional silanes, such as diphenyldimethoxysilane (DPDMS), diphenyldiethoxysilane (DPDES) and dimethyldiethoxysilane (DMDES). The effect of TiO2 content in the solution on the refractive index of system was discussed in detail. The result shows that the refractive index of solution increases linearly with TiO2 content. The refractive index of the three hybrid nanorneter materials attained 1.6053, 1.5846 and 1.5346, respectively. The size of nanometer particles was characterized by TEM and the particle diameter thus obtained is in the range of 20-90 nm. FT-IR spectra of the materials show that the TiO-Si bond is formed.     

Ag-TiO2纳米催化剂的制备、表征及环氧化催化性能

环氧化合物是一类重要的有机合成中间体。工业上环氧乙烷是以Ａｇ ＳｒＯ ＣａＯ作催化剂 ,通过多相催化由乙烯和氧气氧化得到 ,其它的Ｃ2以上烯烃不能用该法生产 ,因为反应温度高 ,选择性很差。高温下的银催化乙烯的分子氧环氧化 ,选择性高于 80 % ,而用于丙烯的环氧化时 ,选择性大大降低[1] ,银多相催化分子氧环氧化烯烃的研究较活跃[2 5] 。本文合成了Ａｇ ＴｉＯ2 纳米催化剂 ,对其进行了表征 ,并初步研究了其环氧化催化性能。1　实验部分1 .1　仪器药品ＴｅｓｔｓｃａｎＳｈｉｍａｄｚｕＦＴＩＲ 80 0 0ｓｅｒｉｅｓ红外光谱仪 (ＫＢ…     

微乳法合成纳米SiO2/TiO2及其光催化性能

采用聚乙二醇辛基苯基醚(Triton X-100)/正己醇/环己烷/氨水微乳体系合成了纳米TiO2和SiO2/TiO2复合物,用X射线衍射、红外光谱和透射电镜对其结构进行了表征,并以甲基橙降解评价了其光催化性能,讨论了SiO2/TiO2摩尔比、晶相组成及粒径与光催化活性的关系.结果表明,SiO2/TiO2催化剂中形成了新的Ti-O-Si键和无定形SiO2;在纳米TiO2中复合SiO2能有效抑制锐钛矿向金红石的转变,增加锐钛矿的稳定性,并阻止TiO2晶粒的聚集生长.催化剂的光催化活性随金红石含量的增加而降低,加入适量SiO2能明显提高TiO2的光催化活性,其中摩尔比为1/7的SiO2/TiO2光催化活性最高.     

Synthesis and photocatalytic activity of mesoporous TiO(2) with the surface area, crystallite size, and pore size

Mesoporous TiO(2) materials with various pore-size distributions were synthesized by using diblock copolymers via a sol-gel process in aqueous solution. The properties of these materials were characterized by FE-SEM, HR-TEM, XRD, DRS, BET, and BJH analysis. All particles have spherical morphology with a diameter range of 1-3 mum. The mesoporous TiO(2) materials calcined at 400 degrees C were found to have different specific surface areas - 186, 210, and 192 m(2) g(-1) - and average pore sizes depending on the type of diblock copolymer-5.1, 6.1, and 6.4 nm-and their crystallite sizes were found to be 8.1, 8.3, and 8.8 nm. The photocatalytic activity of each sample was investigated by measuring the photodecomposition of methylene blue (MB), and the small crystallite size, large surface area, and small pore size were found to exhibit better photocatalytic activities. In addition, the photocatalytic activities of all the mesoporous TiO(2) materials were found to be better than that of commercial TiO(2).     

掺铈纳米TiO2薄膜制备及光催化降解甲醛甲苯

通过Sol-Gel工艺在玻璃表面及多孔陶瓷表面制得了均匀透明的掺铈纳米TiO2薄膜．通过SEM、XRD及UV-Vis等手段对玻璃表面掺铈纳米TiO2薄膜进行了表征．结果表明，薄膜表面无开裂现象、膜内部比表面积大、TiO2分布均匀．薄膜中出现的锐钛矿相在(101)面有一定的择优取向，且UV-Vis研究表明，掺铈纳米TiO2薄膜在近紫外的吸光度有明显提高．利用自行设计的反应器，以多孔陶瓷为介质，对甲醛、甲苯等有机物进行了光催化降解研究．结果表明，掺铈纳米TiO2薄膜对甲醛甲苯有极高的光催化降解效率，由于薄膜成本低廉，易于工业化，为净化室内空气开辟了新的途径．     

Effect of initial precursor concentration on TiO2 thin film nanostructures prepared by PCVD system

TiO₂ thin film was prepared on Si substrate by plasma chemical vapor deposition (PCVD) system and the morphologies of TiO₂ thin film were controlled by adjusting the initial precursor concentration. As the initial titanium tetra-isopropoxide (TTIP) concentration increases in PCVD reactor, the shapes of TiO₂ particles generated in PCVD reactor change from the spherical small-sized particles around 20 nm and spherical large-sized particles around 60 nm to aggregate particles around 100 nm. The TiO₂ particles with different shapes deposit on the substrate and become the main building blocks of resulting TiO₂ thin film. We observed the TiO₂ thin film with smooth morphology at low initial TTIP concentration, granular morphology at medium initial TTIP concentration, and columnar morphology at high initial TTIP concentration. It is proposed that we can prepare the TiO₂ thin film with controlled morphologies in one-step process just by adjusting the initial precursor concentration in PCVD.     

Mg-Al 类水滑石/二氧化钛异质复合纳米晶光催化氧化苯的性能

 采用过饱和沉淀法合成 n(Mg)/n(Al) = 2 的 Mg-Al 类水滑石化合物 (Mg-Al-HT), 再用水热法将它与钛胶复合, 制得 Mg-Al-HT/TiO2 异质复合光催化剂. 采用 X 射线粉末衍射、透射电子显微镜、场发射扫描电子显微镜、低温 N2 吸附-脱附、紫外-可见漫反射光谱和热重等技术对催化剂结构、成分和性质进行了表征. 结果表明, 在波长 365 nm 的紫外光照射降解苯的反应中, Mg-Al-HT/TiO2 异质复合光催化剂表现出优于单一的 TiO2 或 Mg-Al-HT 催化剂的光催化活性, 且稳定性更高; 同时讨论了该复合催化剂性能优异的原因. 另外, 运用电子顺磁共振技术检测到体系中存在羟基自由基等活性物种, 并据此提出了 Mg-Al-HT/TiO2 异质复合纳米晶催化剂光催化降解苯的反应机理.     

纳米TiO2/Si薄膜的制备与光催化性能的研究

1972年, Fujishima等发现受辐射的TiO₂上可以持续发生水的氧化还原反应产生氢, 从此, 半导体光催化受到了重视并得到进一步广泛的研究^[1]。     

Ag／TiO2复合纳米催化剂的制备和表征及其光催化活性

 采用光还原沉积贵金属法，制备了Ag／TiO2复合纳米催化剂．通过调节溶液的pH值控制TiO2表面负载银的形貌，利用AAS，XRD，TEM和XPS等手段对样品进行了表征．以苯胺氧化为模型反应，考察了Ag／TiO2复合纳米催化剂样品的光催化活性以及银沉积量和沉积形貌对催化剂活性的影响．结果表明，通过调控光还原沉积条件，可在平均粒径为24nm左右的TiO2颗粒上获得3nm左右均匀分散的银粒子；在TiO2上沉积适量的具有较高分散度的金属Ag，能有效提高TiO2对苯胺氧化反应的光催化活性．     

Preparation, photocatalytic activities, and dye-sensitized solar-cell performance of submicron-scale TiO2 hollow spheres

We prepared submicron-scale spherical hollow particles of anatase TiO2 by using a polystyrene-bead template. The obtained particles were very uniform in size, with a diameter of 490 nm and a shell thickness of 30 nm. The Brunauer-Emmett-Teller surface area measurements revealed a large value of 70 m2/g. The photocatalytic property was investigated by the complete decomposition of gaseous isopropyl alcohol under UV irradiation. It was indicated that the activity of the hollow spheres was 1.8 times higher than that of the conventional P25 TiO2 nanoparticles with a diameter of 30 nm. Furthermore, we fabricated a dye-sensitized solar cell (DSC) using an electrode of the TiO2 hollow spheres, and examined the photovoltaic performance under simulated sunlight. Although the per-area efficiency was rather low (1.26%) because of a low area density of TiO2 on the electrode, the per-weight efficiency was 2.5 times higher than those of the conventional DSCs of TiO2.     

影响TiO2薄膜光催化降解亚甲基蓝的因素

 用中频交流反应磁控溅射技术制备了具有良好光催化性能的TiO2薄膜,考察了紫外光源、反应器和溶液浓度对亚甲基蓝溶液光催化降解特性的影响. 结果表明,紫外光源对TiO2薄膜光催化降解性能有较大的影响; 在计算光催化降解速率时应充分考虑光解和光氧化的影响. 低压汞灯TUV为光催化降解的较好选择. 动态反应系统可以有效避免光解,显著提高光催化反应速度. TiO2薄膜具有很好的光催化性能,且性能稳定.     

具有高光催化活性的介孔单晶TiO2薄膜的制备

光催化技术在常温下能够直接利用太阳能来驱动反应, 已成为一种理想的环境污染治理和洁净能源生产技术. 但是比较多的限制条件阻碍了光催化发展和实际应用, 如何有效解决这些限制因素成为光催化技术走向工业化应用必须解决的问题. 目前光催化材料研究存在的问题主要包括: (1)研究工作主要集中的粉体催化剂存在分离困难、难以重复利用的缺点, 开发与基底结合牢固的薄膜材料是十分必要的; (2)光催化材料本身的光响应范围影响光催化材料的应用, 拓宽催化剂材料的光吸收范围是亟待解决的; (3)光生电子和空穴的复合问题是影响光催化剂催化活性的主要因素之一, 很多方法被用来阻止电子-空穴对的复合, 如: 金属和非金属的掺杂、贵金属修饰、异质结、新型催化剂结构的设计等, 如何设计促进催化剂光生电子和空穴的分离成为光催化技术应用的重要问题.介孔单晶TiO2通过自组装的方法被制备, 成为TiO2的一种新结构材料. 介孔单晶TiO2结合了介孔材料的大比表面积、单晶材料的电荷传输快等优点, 对于光催化性能有了很大的提高. 目前介孔单晶TiO2主要是以粉体的形式存在, 但是粉体TiO2的应用受到多方面的影响, 如: 难回收不易重复利用, 与电催化结合难, 不能借助电催化提高电荷分离效率等. TiO2薄膜能够解决粉体的不足, 近年来, TiO2光催化薄膜得到广泛的研究, TiO2薄膜的制备方法很多, 主要有液相制备方法、物理气相沉积法、化学气相沉积法、电化学方法、溅射法等. TiO2薄膜主要是以纳米颗粒的形式沉积在基底上, 并且多为多晶和无定形. 而对于介孔单晶TiO2薄膜的制备和研究还没有报道. 我们通过直接焙烧一步法制备了介孔单晶TiO2薄膜, 并对TiO2薄膜的生长情况、表面结构、TiO2晶相和晶体完整程度的变化对性能的影响进行了研究. 通过调变Ti与F的比例和煅烧温度, 研究不同的制备条件对其性能的影响, 从而制备高活性TiO2薄膜. 为了进一步提高介孔单晶TiO2薄膜的活性和拓展其吸收光谱范围, 使用高温热解自组装技术一步法制备了贵金属Au负载的介孔单价TiO2薄膜, Au纳米颗粒跟TiO2有较好的结合度. 在可见光照射下, Au/TiO2异质结构中Au表面由等离子体共振效应产生的活泼电子会注入TiO2导带, 使光生电子和空穴得到分离; 同时Au具有特殊的可见光等离子体共振效应能显著改善TiO2类宽带隙半导体的可见光响应性能.实验用还原Cr(Ⅵ)作为探针反应, 考察不同Au含量对光催化性能的影响.     

Optimizing the photocatalytic properties of hydrothermal TiO2 by the control of phase composition and particle morphology. a systematic approach

The possibility of controlling the photocatalytic activity of TiO2 nanoparticles by tailoring their crystalline structure and morphology is a current topic of great interest. In this study, a broad variety of well-faceted particles with different phase compositions, sizes, and shapes have been obtained from concentrated TiOCl2 solutions by systematically changing temperature, pH, and duration of the hydrothermal treatment. The guide to select the suitable experimental conditions was provided by thermodynamic modeling based on available thermochemical data. By combining the results of TEM, HRTEM, XRD, density, and specific surface area measurements, a complete structural and morphological characterization of the particles was performed. Correlation between the photocatalytic activity in the UV photodegradation of phenol solutions and the particle size was established. Prismatic rutile particles with length/width ratio around 5 and breadth of 60-100 nm showed the highest activity. The surface chemistry of the particles was also investigated. Treatments that decrease the surface acidity, such as washing the powders with ammonia solution and/or calcining at 400 degrees C, have detrimental effect on photocatalytic activity. The overall results suggest correlation between particle morphology and photocatalytic activity and indicate that both electron-hole recombination and adsorption at the surface can be rate-controlling processes. The systematic approach presented in this study demonstrates that a substantial improvement of the photocatalytic activity of TiO2 can be achieved by a careful design of the particle morphology and the control of the surface chemistry.     

Fabrication of hydroxyl group modified monodispersed hybrid silica particles and the h-SiO(2)/TiO(2) core/shell microspheres as high performance photocatalyst for dye degradation

The monodisperse hybrid silica particles (h-SiO(2)) were firstly prepared by a modified sol-gel process and the surface was modified in situ with double bonds, then abundant carboxyl moieties were introduced onto the surface of the silica core via thiol-ene click reaction. Afterward, the h-SiO(2)/TiO(2) core/shell microspheres were prepared by hydrolysis of titanium tetrabutoxide (TBOT) via sol-gel process in mixed ethanol/acetonitrile solvent, in which the activity of TBOT could be easily controlled. The carboxyl groups on the surface of silica particles promote the formation of a dense and smooth titania layer under well control, and the layer thickness of titania could be tuned from 12 to 100nm. The well-defined h-SiO(2)/TiO(2) core/shell structures have been confirmed by electron microscopy and X-ray photoelectron spectroscopy studies. After calcination at 500°C for 2h, the amorphous TiO(2) layer turned into anatase titania. These anatase titania-coated silica particles showed good photocatalytic performance in degradation of methyl orange aqueous solution under UV light.     

TiO2膜光催化剂的改进及表征

提出用粉末-溶胶法制备TiO2薄膜型光催化剂,介绍了粉溶法的制备工艺及改变pH值对催化活性的影响.研究结果表明, 利用粉溶法或添加浓HNO3后制备的TiO2薄膜光催化剂表现出了较高的光催化活性.结合结构表征详细分析了其中的原因.认为粉溶法制备的催化剂表面更粗糙,比表面积增大,膜厚度减小,这些都可能是其催化活性提高的原因.而加酸后膜催化活性提高主要是因为酸性条件下表面几乎没有Ti3+表面态,利于光生电子与光生空穴的分离.