Preparation and characterization of highly photoactive nanocrystalline TiO<Subscript>2</Subscript> powders by solvent evaporationinduced crystallization method

Highly photoactive bi-phase nanocrystalline TiO₂ photocatalyst was prepared by a solvent evaporation-induced crystallization (SEIC) method, and calcined at different temperatures. The obtained TiO₂ photocatalyst was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air. The results show that solvent evaporation can promote the crystallization and phase transformation of TiO₂ at 100°C. When calcination temperatures are below 600°C, the prepared TiO₂ powders show bimodal pore size distributions in the mesoporous region. At 700°C, the pore size distributions exhibit monomodal distribution of the inter-aggregated pores due to the collapse of the intra-aggregated pores. At 100°C, the obtained TiO₂ photocatalyst by this method shows good photocatalytic activity, and at 400°C, its photocatalytic activity exceeds that of Degussa P25. This may be attributed to the fact that the prepared TiO₂ photocatalyst has higher specific surface areas, smaller crystallite size and bimodal pore size distribution.     

二氧化钛柱撑蒙脱土的溶剂热合成及光催化活性

以乙醇水溶液为溶剂,以六亚甲基四胺为沉淀剂,以TiCl3为前驱体,通过醇-水溶剂热的方法合成出二氧化钛柱撑蒙脱土复合纳米光催化剂,通过XRD、BET、AAS等对其物相组成、比表面积及元素含量等进行了表征．结果表明,复合光催化剂具有良好的介孔结构,其孔径分布主要集中在6～10nm,且比表面积明显增大．光催化降解亚甲基蓝活性结果表明,当m（TiO2）／m（蒙脱土）=0．2：1时,复合催化剂由于柱化后具有较大的比表面积、孔容和适当的孔分布而表现出良好的光催化活性．     

Effects of urea on the microstructure and photocatalytic activity of bimodal mesoporous titania microspheres

Bimodal mesoporous TiO₂ microspheres with high photocatalytic activity were prepared by a hydrothermal method using titanium sulfate as precursor in the presence of urea. The results indicate that all prepared samples show bimodal pore-size distributions in the mesoporous region: smaller intra-aggregated pores with peak pore diameter of ca. 2 nm and larger inter-aggregated pores with peak pore diameter of ca. 12.5 nm. The molar ratio of urea to Ti(SO₄)₂ (R_u) has an obvious influence on the morphology, microstructure and photocatalytic activity of TiO₂. With increasing R_u, specific surface areas and porosity increase, contrarily, the crystallite size and relative anatase crystallinity decrease. The photocatalytic activity first increases with R_u. At R_u = 2.0, the photocatalytic activity reaches the highest and is obviously higher than that of Degussa P25. With further increasing R_u, the photocatalytic activity decreases. The formation rate of hydroxyl radicals during photocatalysis has a positive correlation with the photocatalytic activity.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料, 与葡萄糖溶液在220 ℃下进行水热反应, 再在空气中520 ℃焙烧, 制备出介孔TiO2. 用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征. 结果表明, 该介孔TiO2具有微米级棒状或针状形貌, 晶粒大小为12.3 nm, 比表面积为106 m2·g-1, 孔容为0.31 cm3·g-1, 孔径为8.06 nm, 焙烧处理后晶型仍是锐钛矿相. 水热生成的碳抑制了晶粒的团聚生长和晶型的转变, 提高了介孔TiO2的热稳定性. 甲基橙降解实验评价了介孔TiO2的光催化性能, 结果发现其活性与商用TiO2催化剂P25相当, 而其较大的粒径更容易回收再利用. 以碘化钾为探针反应, 表明介孔TiO2的光催化机制以光生空穴氧化为主.     

活性炭孔结构对TiO2/AC复合光催化剂光催化活性的影响

以4种表面化学性质相近, 而孔结构差异较大的活性炭(AC)为原料, 采用酸催化水解法合成了系列TiO2/AC复合催化剂, 考查活性炭孔结构对复合光催化剂活性的影响. 以苯酚为模型物, 考察了催化剂的活性;以低温(77 K)液氮吸附测定活性炭的比表面积、孔容和孔径分布;以Boehm滴定及元素分析定量表征活性炭表面化学性质. 以SEM观测复合催化剂表面TiO2的分散性能;以X射线衍射(XRD)、漫反射光谱(DRS)测试光催化剂晶相结构参数及光吸收阈值. 结果表明, 活性炭孔结构性质对TiO2/AC活性影响显著. AC1、AC2、AC3、AC4对TiO2活性提高的协同系数分别为1.55、2.03、1.28、1.43. 协同系数大小与接触界面面积变化值(⊿S)趋势相似. 具有发达的微孔及适量中孔结构的TiO2/AC复合光催化剂的催化活性最高.     

Ag担载对TiO2光催化活性的影响

 采用光化学沉积法合成了Ag/TiO2光催化剂,以苯酚降解反应考察了光催化剂活性随Ag担载量的变化,用TEM观察了Ag在TiO2表面的分布与形貌,以漫反射紫外-可见光谱(DRS)分析了不同Ag担载量的光催化剂的光谱特征. 结果表明,适宜担载量的Ag可显著提高TiO2的光催化活性. TEM观察显示,Ag在TiO2表面形成纳米级团簇结构,随Ag担载量的增加,团簇尺寸增大. DRS分析表明,Ag的担载对TiO2紫外区域的光谱特征没有影响. 根据Ag团簇的能级随其几何尺寸的变化分析了Ag担载量的变化对TiO2光催化活性的影响机理.     

活性炭负载TiO2光催化氧化二苯并噻吩的研究

以活性炭负载的TiO2为光催化剂,H2O2为氧化剂,30W紫外灯为光源,对含二苯并噻吩（DBT）的模型硫化物进行光催化氧化脱硫研究。考察了TiO2的煅烧温度、负载量、催化剂用量、H2O2用量和光照时间对DBT去除率的影响。实验结果表明,用溶胶 凝胶法制备的TiO2 /活性炭催化剂对DBT具有很好的光催化效果。最佳反应条件为,催化剂煅烧温度400℃,TiO2的负载量为32％,催化剂用量0.7g/100mL, H2O2最佳用量为10mL,即O/S（摩尔比）为14。在最佳反应条件下,光照时间8h,DBT去除率为90％, 此反应为一级动力学反应。     

Photocatalytic Activity of Nanosized ZnWO4 Prepared by the Sol-gel Method

Nanosized ZnWO4 photocatalysts were successfully synthesized via the sol-gel process in a temperature range of 450-800 ℃.The grain size,crystal size,and crystallinity of ZnWO4 particles increased with the increase of calcination temperature and prolonging calcination time.The photocatalytic activity was measured for the degradation of an aqueous Rhodamine-B(RhB)solution and gaseous formaldehyde(FAD).With the increase of calcination temperature and time,the activities increased to a maximum and then decreased.ZnWO4 photocatalyst prepared at 550 ℃ for 10 h showed the highest activity,which is similar to the photocatalytic activity of P25TiO2 for the degradation of gaseous FAD.High crystallinity,large surface area,and good dispersion are responsible for the high photocatalytic performance of the prepared ZnWO4.     

介孔二氧化钛的合成及其对甲基橙降解的光催化活性

以十六烷基三甲基溴化铵为模板剂,通过水解钛酸正丁酯合成了介孔二氧化钛分子筛,探讨了合成条件的影响。采用X射线粉末衍射(XRD)、红外光谱(FT-IR)、透射电子显微镜(TEM)和N2吸附-脱附等技术对介孔二氧化钛的晶相、结构、形貌、比表面积和孔径分布进行了表征。实验结果表明:得到的介孔二氧化钛分子筛的孔径为4-4.3nm,用抽提的方法去除模板剂得到的介孔二氧化钛的比表面积比焙烧的要高。以甲基橙为模型污染物,检验了所合成介孔二氧化钛的光催化性质。     

Gas-phase photocatalytic oxidation of benzene over titanium dioxide loaded on Bi_(12)TiO_(20)

TiO2 was prepared by sol-gel method using tetrabutyl titanate as precursor. TiO2 was loaded on Bi12TiO20. The photocatalyst with different TiO2 loading was calcined at 723 K. The photocatalytic activity of decomposition gaseous benzene was investigated in a batch reactor. The prepared photocatalyst was characterized by UV-vis diffuse reflectance. The result showed that TiO2/Bi12TiO20 absorbed much more ultraviolet light than Ti02 in the ultraviolet light region and showed red shift. The results indicated that the prepared photocatalyst can greatly promote the photocatalytic activity. The 2.0% TiO2/Bi12TiO20 system exhibited the highest photocatalytic activity.     

超临界流体干燥法制备TiO2／C纳米粒子及光催化性能

以TiCl4为原料,采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO2/C复合光催化剂.以苯酚的光催化降解对所得催化剂的催化活性进行了评价.结果表明,纳米TiO2/C复合粒子与单组分TiO2比较,复合粒子光催化活性高于单组分的TiO2,h苯酚降解率高达975 ％,COD为957%.并用XRD、TEM、 UV-Vis和XPS等手段进行了表征,iO2以锐钛矿型形式存在.比较了不同制备方法制得的TiO2/C复合催化剂,得出超临界干燥法制备的光催化剂具有粒径小,比表面积大,分散性好,光催化活性高等特点.     

块状TiO2/SiO2气凝胶的非超临界干燥法制备及其表征

分别通过TiO2和SiO2的单独溶胶和TiO2/SiO2复合凝胶,并添加干燥控制化学添加剂甲酰胺,形成比较完善的凝胶网络结构,同时通过正硅酸乙酯的乙醇溶液浸泡,低表面张力溶剂替换和分级陈化以及干燥等步骤,实现了块状TiO2/SiO2复合气凝胶的非超临界干燥制备.所得TiO2/SiO2气凝胶为无色或乳白色轻质块状多孔固体,表观密度约0.4～0.9g/cm3,孔隙率约80%～95%.它由直径约10nm的TiO2和SiO2微粒相互分散复合而成,孔洞直径约几十纳米.其相态SiO2为无定形,TiO2为锐钛矿晶型.随着焙烧温度的升高,直到800℃不发生相变化.     

球磨法制备复合光催化剂Bi12TiO20/ZnO及其光催化性能

本文用水作为分散介质,采用球磨法掺杂一定量的Bi₁₂TiO₂₀于ZnO中制备复合光催化剂Bi₁₂TiO₂₀/ZnO. 利用UV-Vis、XRD和SEM等仪器对样品进行了分析与表征. 通过对甲基橙的氧化来研究其光催化活性. 结果表明,光催化剂Bi₁₂TiO₂₀/ZnO对甲基橙氧化的催化活性高于氧化锌的催化活性.当Bi₁₂TiO₂₀的掺杂量为0.5%(质量分数),球磨时间为12 h,焙烧温度为300℃时,光照20 min后,复合光催化剂Bi₁₂TiO₂₀/ZnO对甲基橙的降解率可达到95.2%.     

Au掺杂方式对锐钛矿TiO2光催化性能的影响

结合超临界乙醇干燥技术, 采用沉积-沉淀(DP)和共沉淀(CP)法分别制备了具有单一锐钛矿晶相的Au/TiO2和Au(0.2%, 原子分数)-TiO2光催化剂, 通过XRD、BET、TEM、XPS和Raman手段表征样品中Au的掺杂形态, 以光催化降解甲基橙为模型反应考察了样品的光催化活性. 结果表明, DP法制备的Au/TiO2在110 ℃干燥处理后, 表面存在的Au3+能有效地促进锐钛矿TiO2光催化性能, 其一级反应速率常数比纯锐钛矿TiO2提高了3.2倍, 比商用光催化剂Degussa-P25提高了4.1倍, 而当Au3+被还原为Au0后光催化活性下降. 用CP法制备的Au-TiO2并没有较大地提高锐钛矿TiO2光催化性能, 在焙烧温度达到800 ℃时, Au向表面迁移聚集, 造成锐钛矿TiO2晶格氧空位和缺陷位增加, 使光催化活性下降.     

Low Temperature Solvent Evaporation-induced Crystallization Synthesis of Nanocrystalline TiO2 Photocatalyst

A novel and efficient methodology for obtaining highly active photocatalyst of bi-phase TiO2 with small particle size and high specific surface area was developed by solvent evaporation-in-duced crystallization (SEIC) method at low temperature. The prepared TiO2 powder was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalyfic activity was evaluated by the photocatalyflc oxidation of acetone in air. The results showed that the photocatalytic activity of the TiO2 powder preDared by this method approached that of Degnssa P25. This may be atotributed to the fact that the predated TiO2 powder had larzer specific surface areas (265 m2. g- 1 ) and smaller crystallite size (about 5 nm), but relatively low crystallinity, as compared with Degussa P25.     

Preparation of bimodal micro-mesoporous TiO2 with tailored crystalline properties

A new mild crystallization procedure has been applied after a synthesis route in the presence of a non-ionic surfactant, leading to the preparation of bimodal micro-mesoporous TiO2, with remarkable textural properties and pore walls formed by anatase nanocrystals, which exhibit photocatalytic activity.     

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."     

高活性低失活In(OH)3纳米晶光催化剂的制备和表征

采用超声沉淀法从In(NO3)3制备出了In(OH)3纳米晶体, 发现其在254 nm紫外光照射下对苯催化活性和活性稳定性比P25-TiO2高得多.     

双介孔结构的纳米TiO2/I2复合材料的制备及其可见光催化性能

以钛酸丁酯为前驱体,碘溶胶为碘源,在室温下采用水解沉淀法制备了单质碘和纳米TiO2复合的双介孔结构光催化剂(M-I2-TiO2).采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I2-TiO2进行了表征.以次甲基蓝(MB)溶液为模拟废水,对M-I2-TiO2的光催化性能进行了评价,研究了不同热处理温度对光催化活性的影响.结果表明,M-I2-TiO2在可见光区有显著的吸收,300℃热处理得到的样品比表面积高达227.6 m2/g,600℃热处理所得样品的比表面积仍高达111.8 m2/g,而400℃热处理所得样品具有最好的光催化降解性能.双介孔结构纳米TiO2/I2复合材料的光催化降解性能显著高于相同方法制备的纯TiO2和Degussa P-25商业产品.催化剂经6次重复使用其光催化活性基本保持不变.     

碘掺杂对纳米TiO2催化剂光催化活性的影响

用溶胶-凝胶法制得了碘掺杂纳米TiO2催化剂, 考察了诸因素对相结构的影响, 这对深入揭示I-TiO2光催化降解有机物的本质具有重要意义.