不同介质中水热合成纳米TiO2粉体及其光催化性能研究

以钛酸四丁酯为原料,采用水热法分别以蒸馏水、有机小分子化合物(正丁醇、丙二酸和乙二胺水溶液)和无机酸(HNO3、H2SO4和HCl)为介质合成了TiO2纳米粉体.通过XRD和TEM对所得TiO2粉体进行了表征,研究不同介质对所得TiO2粉体的晶相组成、颗粒尺寸及形貌的影响.结果表明:以蒸馏水为介质时所得锐钛矿TiO2的颗粒尺寸分布不均匀;有机化合物抑制锐钛矿型TiO2各向异性生长趋势的能力为:正丁醇＞丙二酸＞乙二胺;相同实验条件下,HCl、H2SO4及HNO3体系中分别获得金红石、锐钛矿及锐钛矿和金红石混晶TiO2.光催化降解甲基橙的研究表明,锐钛矿和金红石混晶TiO2的光催化活性要高于纯锐钛矿结构;纯金红石型TiO2的光催化活性最差.     

双微乳液法制备掺杂Fe~(3+)的纳米TiO_2及其光催化性能

为了研究双微乳液法在制备纳米级光催化剂的应用,以TiCl4和NH3.H2O为原料,采用十六烷基三甲基溴化铵-正丁醇-环己烷-水微乳体系制备Fe3+掺杂纳米TiO2,对粉末的晶体结构进行X射线衍射表征,并以其对p-甲酚的降解考察其光催化活性。结果表明,在较小的掺杂量时,Fe3+掺杂量的提高可以提高TiO2的光催化活性,进一步提高掺杂量将引起光催化活性的降低;掺杂Fe3+可导致纳米TiO2的粒径减小;Fe3+的半径较小以及Fe2O3的熔点较低均有利于TiO2从锐钛矿向金红石的相变;当Fe3+掺杂摩尔分数为0.06%,煅烧温度为550℃时,纳米TiO2的光催化活性最高,此时形成TiO2的锐钛矿和金红石相的混晶;乳液中含水量也会影响晶相的组成和粒径大小,随着含水量增加产物中出现了一定比例的金红石相。     

混晶结构纳米TiO2粉的光催化活性

以钛酸四丁酯为钛源制备混晶结构纳米TiO2粉,研究了纳米TiO2的光催化活性与颗粒晶相结构之间的关系．结果表明,当金红石相的质量分数少于18．53％,光催化活性随着金红石相的增多而降低;当金红石相的质量分数为18．53％-28．2％时,随着金红石相的增多,光催化活性逐渐增强,在28．2％附近具有最高的光催化活性,与纯锐钛矿结构纳米TiO2粉的光催化活性相当;金红石相含量继续增加,则光催化活性逐渐降低．适量金红石相的存在有利于锐钛矿相中的电荷分离,使光催化活性提高．     

纳米二氧化钛的晶型转变及光催化性能研究

采用溶胶-凝胶法制得稳定的TiO2透明溶胶．凝胶经焙烧制备了纳米TiO2粉体,利用FT-IR、XRD和原子力显微镜(AFM)技术对其进行了结构和形貌表征,考察了其对水杨酸的光催化活性。研究结果表明,醇胺不同的加入量,对TiO2从锐钛矿转变为金红石型的晶相转变温度(600～800℃)有很大影响．FT-IR谱的423cm^-1处吸收峰为金红石型TiO2的特征Ti-O键振动峰,采用310nm的紫外光波长照射时锐钛矿型TiO2粉体具有较高的光催化活性。     

二氧化钛纳米晶的制备及光催化活性研究

本文用溶胶—凝胶法制备了不同晶相的TiO2纳米晶，将其负载于镍网上，以苯酚的降解为模型反应，研究对比了不同晶相TiO2纳米晶的光催化活性。结果表明，纯锐钛矿相的TiO2纳米晶的降解能力要强于锐钛矿与金红石混合相的TiO2纳米晶。     

低温制备锐钛矿型TiO2溶胶的性能研究

采用溶胶-凝胶法,以水为溶剂,在低于70℃下直接合成纳米锐钛矿型TiO2溶胶,研究了反应温度、pH值对溶胶晶型、晶粒大小和稳定性的影响.以不同光照下对亚甲基蓝的降解,评价了溶胶的光催化活性.结果表明:较低pH值下溶胶中的TiO2出现了金红石相与锐钛矿相组成的混晶相,而pH值相对较高时则得到纯锐钛矿相TiO2;在紫外光、日光灯和太阳光下,与P25对亚甲基蓝的降解相比,同等条件下所制备的TiO2溶胶显示出更好的光催化活性;混晶相TiO2溶胶的光催化性优于纯锐钛矿相TiO2溶胶.     

二氧化钛催化剂晶型调控技术的研究进展

综述二氧化钛由锐钛矿向金红石晶型转变调控技术的最新成果,分析温度、氧化物和以及离子掺杂对实现晶型转变的影响规律,重点研究氧化物和离子掺杂对晶型转变的影响。结果显示:复合金属氧化物熔点低于TiO2熔点时,可促进锐钛矿型TiO2向金红石型转变;而金属氧化物熔点高于TiO2熔点时,可阻碍晶型转变;掺杂离子的离子半径、化合价、离子大小对二氧化钛晶型转变及催化性能有明显的影响,当掺杂金属离子半径大于或小于Ti4+半径,使得锐钛矿型TiO2更稳定;当掺杂离子的半径与Ti4+半径相近时,有利于锐钛矿型向金红石型转变,而体积较小的低价阴离子有利于金红石型二氧化钛的的生成,体积较大的高价阴离子则有利于锐钛矿型二氧化钛的的生成;阴阳离子共掺杂可以有效地调控二氧化钛晶型转变,并且能够提高TiO2的光催化活性。探讨二氧化钛多晶之间的协同作用,并基于二氧化钛掺杂改性的计算模拟,指出今后的发展方向。     

TiO_2自组装膜的制备及抗菌性能研究

以TiCl4为主要原料,采用自组装工艺,在玻璃基底表面制备TiO2薄膜。考察了(NH4)2SO4的添加、热处理温度、TiCl4浓度、反应温度、反应时间等工艺参数对TiO2薄膜结构和抗菌性能的影响规律。结果表明:未添加(NH4)2SO4时生成金红石型TiO2,而添加(NH4)2SO4可生成锐钛矿型TiO2,并且有利于TiO2膜均匀沉积。升高热处理温度,提高了TiO2的结晶度和薄膜附着力。但是,晶型和结晶度对薄膜的抗菌性能没有显著影响。随着TiCl4浓度增加,反应温度提高和反应时间延长,TiO2薄膜的抗菌性能得到提高。在最佳工艺条件,热处理温度为600℃、TiCl4浓度为0.2mol/L、反应温度为80℃、反应时间为80min时,抗菌率达100%。     

可剥离TiO2纳米管光催化共去除酸性橙7和Cr（Ⅵ）的性能研究

以0.5%（质量分数）NH4F/HF/乙二醇为电解液,采用恒压二次阳极氧化法制备出高度有序的可剥离TiO2纳米管阵列,并对其晶型、形貌以及光催化性能等方面进行了研究。通过XRD测试,可知样品经500和800℃退火,分别得到锐钛矿和金红石型TiO2纳米管;通过SEM表征,可知所制备的TiO2纳米管管径约为100nm,管长约为25μm。在紫外光照射下,以TiO2纳米管阵列为催化剂,对其光催化降解酸性橙7（AO7）和Cr（Ⅵ）混合水溶液进行了研究。考察了不同晶型、pH值、不同酸性橙7和Cr（Ⅵ）初始浓度对光催化性能的影响。结果表明锐钛矿型样品光催化性能高于金红石型,三元体系TiO2/AO7/Cr（Ⅵ）中,协同效应显著,酸性条件下尤其有利于TiO2纳米管阵列光催化共去除AO7和Cr（Ⅵ）。     

低温制备混晶TiO2纳米粒子及其光催化性能研究

通过低温液相合成混合晶型纳米TiO2颗粒,研究纳米TiO2颗粒的光催化活性与颗粒晶相组成之间关系.用XRD对其进行表征,并在紫外光下,以甲基橙光催化降解为模型反应,研究了不同晶相样品的光催化活性.结果表明:混合晶相中锐钛矿质量分数占69.8%、金红石质量分数占30.2%,TiO2光催化效用最好可达95.7%.     

Solvothermal synthesis of crystalline phase and shape controlled Sn(4+)-doped TiO2 nanocrystals: effects of reaction solvent

The Sn(4+)-doped TiO(2) nanocrystals with controlled crystalline phase and morphology had been successfully prepared through easily adjusting the solvent system from the peroxo-metal-complex precursor by solvothermal method. The Sn(4+)-doped TiO(2) nanocrystals were characterized by XRD, Raman, TEM, HRTEM, XPS, ICP-AES, BET, and UV-vis. The experimental results indicated that the Sn(4+)-doped TiO(2) nanocrystals prepared in the pure water or predominant water system trend to form rodlike rutile, whereas the cubic-shaped anatase Sn(4+)-doped TiO(2) nanocrystals can be obtained in the alcohol system. The growth mechanism and microstructure evolution of the Sn(4+)-doped TiO(2) nanocrystals prepared in the different solvent systems are discussed. The liquid-phase photocatalytic degradation of phenol was used as a model reaction to test the photocatalytic activity of the synthesized materials. It was found that sample Sn(4+)-doped TiO(2) prepared in 1-butanol showed the maximum photoactivity, which attributed to higher band gap, optimal crystalline phase and surface state modifications.     

TiO_2纳米粒子的结构、表面特性及其光催化活性研究

采用金属醇盐水解法制备了ＴiＯ２纳米粒子,并用ＸＲＤ、ＳＰＳ、ＸＰＳ和ＥＳＲ等测试手段对ＴiＯ２粒子进行结构、性能测试．随焙烧温度的增加,ＴiＯ２粒子长大,晶型由锐钛矿向金红石型转变．以庚烷的气相光催化氧化为试验反应,考察不同温度处理的醇洗、水洗ＴiＯ２粒子的光催化活性．结果表明,醇洗粒子较水洗粒子显示出高的光催化活性,并且低温处理的粒子其光伏响应带边蓝移明显;阈值增加,Ｔｉ３＋含量较高,光催化活性增加．     

二氧化钛纳米晶的光催化活性研究

以苯酚的光催化降解为模型反应,研究了锐钛矿相和金红石相二氧化钛纳米晶（７￣４０ｎｍ）的光催化活性。与市售的氧化钛相比,两种晶相的纳米氧化钛均有很高的光催化活性,锐钛矿相氧化钛对苯酚的深度矿化有更高的选择性。ＴｉＯ２吸附的水及羟基会降低氧化钛的光催化活性。由于粒径减小使氧化钛的吸收带边界蓝移,粒径小的氧化钛有更高的催化活性,粒径〈１５ｎｍ时,显示出量子尺寸效应。     

Photocatalytic activity of TiO2 doped with boron and vanadium

Boron (B)- and vanadium (V)-doped TiO(2) photocatalysts were synthesized using modified sol-gel reaction processes and characterized by X-ray diffraction (XRD), Raman spectroscopy and N(2) physisorption (BET). The photocatalytic activities were evaluated by monitoring the degradation of methylene blue (MB). The results showed that the materials possess high surface area. The addition of B favored the transformation of anatase to rutile, while in the presence of V, anatase was the only phase detected. The MB degradation on V-doped TiO(2) was significantly affected by the preparation method. In fact while the presence of V in the bulk did not influence strongly the photoreactivity under visible irradiation, an increase of surface V doping lead to improved photodegradation of MB. The degradation of MB dye indicated that the photocatalytic activities of TiO(2) increased as the boron doping increased, with high conversion efficiency for 9mol% B doping.     

稀土掺杂TiO2光催化材料的制备和性能

采用溶胶-凝胶法制备了5种稀土（Pr、Nd、Sm,Eu、Dy）掺杂TiO2光催化薄膜,研究了稀土掺杂量,镀膜层数、烧结温度和烧结时间对光催化活性的影响．结果表明,各因素对材料的催化活性均存在一最佳值．薄膜中仅含TiO2而未见稀土氧化物,除掺锴TiO2薄膜完全由金红石相组成外,其余均由锐钛矿相和金红石相的混晶组成,其中金红石相所占比例较大,薄膜表面均存在大量缺陷;稀土掺杂TiO2薄膜对罗丹明B的光降解率可达89．3％．稀土掺杂TiO2显著提高了TiO2对可见光的响应能力,提高了材料的光催化活性．     

Structural Characteristics of TiO2 Ceramic Coating by Micro-Plasma Oxidation

TiO2 ceramic coatings with thickness of 20 μm were formed on the surface of pure titanium by micro-plasma oxidation. Their micro-structures were investigated by by using X-ray diffraction and their surface images were detected by using scan electronic microscope. There were three kinds of TiO2 coatings, pure anatase type TiO2 phase, mixed phases consisted of rutile type TiO2 phase and anatase type TiO2 phase, pure rutile type TiO2 phase. The coating surface with the pure anatase type TiO2 phase is rough, while the coating surface with the pure rutile type TiO2phase is smooth. The upper coating surface with the mixed type TiO2 phases is anatase type TiO2 structure and the subsurface of the TiO2 coating is rutile type TiO2structure.     

煅烧温度、煅烧时间和Fe3+掺杂量对TiO2光催化性能的影响

以钛酸四正了酯为先驱物,采用溶胶-凝胶法制备了纯TiO2和Fe3+掺杂的纳米TiO2(Fe3+/TiO2)光催化剂,并用XRD、UV-Vis等进行了表征,系统研究了煅烧温度、煅烧时间和Fe3+掺杂量对催化剂在自然光条件下光催化降解甲基橙性能的影响.结果表明,相同煅烧温度下,Fe3+/TiO2的粒径比纯TiO2的粒径小.制备纯TiO2和Fe3+/TiO2的最佳煅烧时间分别为4h和3h,最佳煅烧温度均为773K.适量掺入Fe3+可以显著提高纳米TiO2在自然光条件下的光催化降解活性,Fe3+/TiO2中Fe3+的最佳掺杂量为10.00%,相应的脱色效率为28.37%.     

溶胶-凝胶法制备TiO2粉体及其光催化性能研究

以钛酸丁酯为前驱物,无水乙醇为溶剂,采用溶胶-凝胶法制备了TiO2粉体,并采用紫外分光光度计、XRD等表征手段对TiO2的粒度、晶型结构进行了表征,分析了煅烧温度、TiO2晶型比例、溶液初始pH值等因素对TiO2结构性能及光催化活性的影响.结果表明:TiO2的锐钛矿晶型与金红石晶型的转相温度为700 ℃左右;采用溶胶-凝胶法制备TiO2时,控制溶液的pH值为4,煅烧温度为600 ℃,所得产物晶型全部为锐钛矿;当无水乙醇与钛酸丁酯的体积比为10:1时,产物的粒径为617 nm;且当配制溶液pH值为4,煅烧温度为600℃条件下,煅烧时间为40~60 min时,所制备TiO2的光催化效果较好,降解率较高;当光催化体系的pH值为9、以质量浓度为10 mg/L的亚甲基兰溶液浸泡2 h,TiO2的用量为0.25 g/L时,产物的降解率高达95.3%.     

Ag-Si Co-doped TiO2 photocatalyst synthesized via a nonaqueous method

Ag-Si/TiO2 photocatalysts were synthesized in a nonaqueous system at 140 degrees C, and then annealed at different temperatures. The obtained photocatalysts were characterized by XRD, TEM, BET, TG-DTA, XPS, as well as UV-vis DRS. The results showed that All Ag-Si/TiO2 held an anatase phase and high thermal stability and the phase transformation from anatase to rutile was retarded to about 900 degrees C. The Ag-Si/TiO2 particles were highly mono-dispersed and the particles size became smaller compared to TiO2. Additionally, UV-vis light absorption shifted to visible region after Ag doping. Si weaved into the matrix of TiO2, while Ag dispersed on the surface of TiO2 particles. The visible light photocatalytic activity was evaluated by Rhodamine B (RhB) degradation in an aqueous solution under visible light irradiation. It was found that the photccatalytic activities of the obtained Ag-Si/TiO2 samples were all higher than those of pure TiO2 and Ag/TiO2, reaching the maximum at the Ag and Si content of 0.5 mol% and 20.0 mol%, respectively. The enhanced visible photocatalytic activity may be attributed to the simultaneous effects of silver and silicon co-doping.