天然矿物负载纳米TiO2研究进展

介绍了负载纳米TiO2光催化剂所用的矿物载体以及负载方法的研究进展，评述了各载体的特点，并展望了负载型光催化剂的研究发展方向。     

负载型TiO2/硅藻土复合光催化剂的研究

以四氯化钛为原料采用溶胶-凝胶法制备了负载型TiO2，硅藻土复合光催化剂，并通过XRD，IR，SEM等手段对样品进行了表征。实验中分别以300W高压汞灯和太阳光为光源，研究了硅藻土载体上TiO2负载量不同对甲基橙溶液光催化氧化效果的影响。实验结果表明：复合光催化剂的催化性能随着TiO2负载量增大先提高，而后有所下降，其中以1g硅藻土与1．8ml四氯化钛制备的TiO2，硅藻土复合催化剂光催化活性最高。     

竹活性炭比表面积及其孔径对TiO2/BAC光催化降解甲醛性能的影响

[目的]研究竹活性炭比表面积及其孔径对TiO2/BAC光催化降解甲醛性能的影响.[方法]以竹子为原料,按照不同浸渍比,用磷酸活化法制备不同孔径和比表面积的系列竹活性炭(BAC)作为载体;通过溶胶凝胶法制备负载型光催化剂(TiO2/BAC),以水溶液中的甲醛作为目标污染物,考察所得的一系列负载型光催化剂的光催化性能;采用氮气吸附、SEM 进行表征,研究了竹活性炭的孔径和比表面积对负载型光催化剂性能的影响.[结果]竹活性炭吸附和TiO2光解的协同效应使TiO2/BAC光催化剂对水溶液中甲醛的处理效率显著提高;比表面积较大、微孔较多、平均孔径为2～3 nm的竹活性炭有利于TiO2的负载,制备得到的复合光催化活性较高.[结论]为TiO2光催化剂的固化负载研究提供了理论依据.     

混晶纳米TiO2光催化性能及混晶相间的机理研究

采用溶胶-凝胶法制备混晶纳米TiO2和珍珠岩负载纳米TiO2混晶催化剂,以XRD、SEM、UV-vis DRS和电化学方法对样品进行表征.结果表明,晶型调节剂的含量对混晶中金红石和锐钛矿相TiO2的比率有较大的影响;对于负载型纳米TiO2催化剂,混晶比影响催化剂的光催化降解效率.并讨论了混晶的光催化机理.     

活性炭负载TiO_2改性处理及其性能表征

采用溶胶–凝胶法对盐酸预处理后的活性炭(activatedcarbon,AC)进行负载TiO2改性处理,利用扫描电镜(SEM)、能谱分析(EDS)、比表面积及孔径测试(BET)、热重分析(TG/DTG)、傅立叶红外光谱分析(FTIR)等对负载TiO2前后的活性炭结构与理化性能进行表征,并利用电化学工作站测试其电化学性能。结果表明,凝胶的最佳煅烧温度为450℃,制得的TiO2/AC复合体表面及孔道中有絮状或颗粒状的TiO2存在,Ti元素含量(质量分数)为24.91%,晶体类型为锐钛矿型;同时,TiO2/AC表面形成一些Ti—O键的含氧官能团。活性炭负载TiO2改性后,比表面积降低23.1%,比电容升高16.4%,电吸附性能提高,可作为电极材料用于去除废水中的无机盐离子。     

超声辅助分子自组装法合成硅胶负载TiO2光催化剂

超声辅助分子自组装法制备表面均匀和高催化活性的硅胶负载TiO2（TiO2-SiO2）光催化剂。采用XRD、SEM、FT-IR、PL等手段对制备产物晶型及形貌等进行了表征。以降解水中偶氮染料甲基橙为探针反应,评价了TiO2-SiO2的光催化活性。结果表明,500℃煅烧TiO2-SiO2的光催化活性最佳。     

聚合物稳定的Au-Pd/TiO2-Al2O3催化剂的还原方法及其催化性能的研究

以PVP为稳定剂，乙醇和K1BH4为还原剂制备了Au-Pd／TiO2-Al2O3催化剂，考察了还原剂对Au-Pd负载型双金属催化剂加氢脱硫性能的影响，并运用XRD，TPD，TPR等技术对催化剂进行表征。结果表明，以乙醇还原的Au-Pd／TiO2-AlO3催化剂的加氢脱硫活性较好。乙醇还原的Au-Pd／TiO2．Al2O3催化剂中Au-Pd之间及活性组分与载体之间的相互作用较强，形成Au-Pd，合金的晶粒较小，活性组分的分散度和活性表面积较大，反应活化能较低，这些均有利于催化剂活性的提高。     

一种磁性内核锐钛型TiO2光催化剂的制备与研究

在水处理技术领域,TiO2光催化水处理技术因具有效率高、能耗低、适用范围广、反应条件温和等优点而被认为是最有前景的有机污染废水处理技术之一。直接应用TiO2悬浮体系处理污水要比基体负载固定TiO2体系有更高的处理效率,但是悬浮态的TiO2存在着回收困难的问题。对此,首先采用了共沉淀-水浴法制备了具有较好形貌的MnxZn1-xFe2O4软磁体颗粒,该软磁体颗粒能够在700℃以内保持良好的磁响应性;采用溶胶-凝胶法在颗粒上包覆SiO2中间层,得到了单分散球形的SiO2/MnxZn1-xFe2O4;采用水热法在其上包覆纳米锐钛型TiO2,最终得到了TiO2/SiO2/(MnxZn1-xFe2O4)磁性光催化剂,采用XRD、SEM、VSM等对其分析,结果表明:该催化剂呈单分散球形,粒径约在500 nm左右,具有明显的壳-核结构,磁性内核被SiO2严密包覆,锐钛型TiO2均匀负载其上,有灵敏的磁响应性。对毛用活性黄废水的降解实验证明了其较高的光催化活性。     

纳米TiO2/SnO2粉体的溶胶-凝胶法制备研究

以有机、无机盐为原料，通过加入稳定剂、催化剂，采用溶胶一凝胶法制备了TiO2、SnO2和TiO2／SnO2纳米微粒，采用XRD、SEM和XPS等技术对粒子的结构和组成进行分析，研究结果表明：TiO2／SnO2粒子主要由锐钛矿型TiO2和金红石型SnO2组成，与纯TiO2、SnO2相比，TiO2／SnO2微粒的粒度小、分布均匀、不团聚。     

负载型TiO2催化剂对提高老龄化垃圾渗滤液可生化性处理效果的研究

本文针对在不同条件下的光化学氧化处理高浓度垃圾渗滤液，进行了改善其可生化性与提高NH3～N去除率的研究。在负载型TiO2催化剂催化下BOD5／CODCr，值从0、064提高到0，228，超过了0.1的可生化性要求。二氧化钛催化剂对NH3-N去除效果明显，15minNH3-N去除率可达80.19％。     

Photocatalytic Activity of Nanosized TiO2 Enhanced by co-doping with Fe3+ and Nd3+ Ions

In this study, nanosized TiO2 co-doped with Fe3 and Nd3 ions was synthesized via a sol-gel method. The metallic ion doped TiO2 was thoroughly characterized with XRD and UV-vis, and the photocatalytic activity was evaluated by degrading methylene blue (MB) solution. The results indicated that TiO2 crystalline size was reduced and phase transformation of anatase to rutile was suppressed as the content of doped Nd3 ion increased in the co-doped TiO2. The UV-vis spectra of co-doped TiO2 seemed to simply overlay two spectra of single metal doped TiO2, and had significantly increased absorbance in the ranges of 400~500 nm, 565~600 nm and 730~765 nm as compared to pure TiO2. The photocatalytic activity of co-doped TiO2 was obviously enhanced, and raised about 30% compared to that of pure TiO2 as doped Nd3 content was 0.15% and Fe3 content was 0.05%, respectively. The enhanced catalytic activity was attributed to a synergistic effect of two doped ions, where doped Fe3 ion inhibited the recombination of photogenerated electron and hole, and Nd3 ion brought more surface carboxyl to promote the degradation reaction.     

Effect of Yb2O3 Additive on Transformation Behavior of Anatase for TiO2/( O'' + β'' )-Sialon Multi phase Ceramics

TiO2/(O' β')-Sialon multiphase ceramics were prepared with nano Ti O2 (anatase) powder and (O' β')-Sialon powder as raw materials. Effect of Yb2O3 additive on transformation behavior of anatase for TiO2/(O' β')-Sialon multi phase ceramic was investigated and its influence mechanism was discussed. XRD was employed for the analysis of phase composition and lattice parameters. The results show that even though Yb2O3 has no obvious influence on starting temperature of phase transformation, it significantly accelerates the transformation process, which displays a weakened effect with more Yb2O3 addition. There exist two forms of the added Yb2O3: some enters TiO2 lattice and the other deposits on the surface of TiO2. The function of Yb2O3 on phase transformation of anatase can be attributed to the coaction of active and negative influence mechanisms as follows: some Ybn enter TiO2 lattice and replace Ti4 , as well as the redox reaction between Yb3 and TiO2, which promote the transformation, whereas other Yb2O3 deposits on the surface of TiO2, and TiO-Yb bond is formed by the coaction of Yb3 and TiO2, which inhibit the process.     

N掺杂二氧化钛纳米管的制备及光催化性能研究

采用阳极氧化法在纯钛表面制备了二氧化钛纳米管,并在热处理的过程中提供氨气氛进行掺N。场发射扫描电镜(FESEM)观察结果表明,制得的纳米管管径为70～80 nm,壁厚为5～10 nm;XRD分析结果表明,400℃热处理的未掺杂二氧化钛为纯锐钛矿相,400℃热处理掺杂后的二氧化钛为锐钛矿和金红石混相。以甲基橙为参考污染物,采用分光光度计研究了未掺杂和N掺杂二氧化钛纳米管对污染物的光催化性能。结果显示N掺杂的二氧化钛纳米管的光催化性能比未掺杂的提高了11.1%,光催化效果差异是N掺杂引起的。     

溶胶 - 凝胶法制备 TiO2 及其冷喷涂性能研究

冷喷涂陶瓷涂层的现有研究表明, 大部分商业陶瓷粉末不适合用于冷喷涂, 而实验室制备的纳米团聚粉末 更易于冷喷涂。 溶胶 - 凝胶法是制备纳米 TiO2 最常用的方法之一, 具有工艺简单、 重复性高、 反应易控制等优点, 而且可以通过实验参数的改变从分子水平对反应进行控制, 从而获得结构形态各异的纳米粒子。 本文采用基于钛 酸四正丁酯水解反应的溶胶-凝胶法制备纳米锐钛矿TiO2, 研究粉末的微观结构并考察其冷喷涂性能, 在此基础上, 分析原料粉末性能对其冷喷涂性能的影响。 研究结果表明, 与商业 TiO2 粉末相比, 溶胶 - 凝胶法制备的 TiO2 粉 末具有良好的冷喷涂工艺适应性。 溶胶 - 凝胶法制备的 TiO2 粉末微观结构为不规则形, 经过热处理后由无定形态 转变为锐钛矿相。 冷喷涂 TiO2 涂层晶体结构及涂层内部 TiO2 颗粒的微观形貌均与溶胶 - 凝胶 TiO2 粉末保持一致。 冷喷涂 TiO2 涂层的光催化活性受原始喷涂粉末影响, 当原始喷涂粉末的光催化活性高时, 冷喷涂 TiO2 涂层的光 催化活性也较高。     

Er3+∶YAlO3/Fe掺杂TiO2复合物的制备及光催化活性研究

对TiO2半导体材料进行改性,分别通过溶胶凝胶、超声波分散和溶液沸腾的方法合成了Er3+∶YAlO3/Fe掺杂TiO2复合物光催化剂,并且采用XRD和SEM进行表征,研究了各种因素在太阳光照射下降解酸性红B的催化活性,也考察了Er3+∶YAlO3的包覆量、Er3+∶YAlO3/Fe掺杂TiO2的量、太阳光照射时间、酸性红B的初始浓度和氯化钠浓度等其降解过程用UV-Vis光谱进行检测。实验结果表明,加入上转光剂之后降解率大幅度增加,改性后的光催化剂可以有效地降解染料废水。     

磁性TiO2空心球的制备及其光催化性能

分别制备Fe3O4和ZnFe2O4粉体并以它们作为磁芯,葡萄糖为模板剂,氟钛酸铵为钛源,通过水热法制备出Fe3O4/C/TiO2和ZnFe2O4/C/TiO2前驱体,煅烧后获得磁性Fe3O4/TiO2和ZnFe2O4/TiO2空心球。采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱仪分析了产物的形貌、结构和化学组成,用振动样品磁强计测试了样品的磁化强度。结果表明,以Fe3O4为磁芯得到的Fe3O4/TiO2空心球的比饱和磁化强度是ZnFe2O4为磁芯得到的ZnFe2O4/TiO2空心球的20倍。以亚甲基蓝溶液为降解模型,考察了磁芯Fe3O4添加量对Fe3O4/TiO2空心球在紫外光下的催化降解能力。结果显示,Fe3O4的添加量对Fe3O4/TiO2空心球的光降解性能影响较小,且Fe3O4/TiO2空心球的紫外光降解能力均比纯TiO2空心球略低,但Fe3O4/TiO2空心球具有在外加磁场下易于回收的优势,具有潜在的应用前景。     

TiO2对含钛高炉初渣物相转变与黏度的影响

为了研究含钛高炉初渣的形成过程和各种物相成分相互作用、迁移重组的过程,明晰TiO2对高炉初渣形成的影响规律,利用FactSage热力学软件及旋转柱体式黏度仪研究了TiO2质量分数对高炉初渣熔化温度、物相转变行为以及初渣黏度的影响。结果表明,随着初渣中TiO2质量分数的增加,含钛高炉初渣熔化温度升高,TiO2质量分数从4%增加到16%,其熔化温度从1 360升高到1 410 ℃,增加了50 ℃;含钛高炉初渣中TiO2质量分数对初渣中各种物相组成的转变和比例都有较大的影响,随着TiO2质量分数的增加,初渣固液相共存的温度区间变大,使高炉软融带变宽;TiO2对含钛高炉初渣黏度的影响相对较为复杂,当TiO2质量分数为4%～8%时,含钛高炉初渣黏度 温度曲线呈现出“碱性渣”的形态;当TiO2质量分数为16%时,含钛高炉初渣黏度 温度曲线呈现出“酸性渣”的形态。     

低温无模板法制备Tio2空心球及其光电性能

基于Ostwald熟化作用的机理,采用无模板法,在低温水热条件下制备了TiO2空心球（TiO2-HS）。探讨了水热反应时间和表面活性剂的种类对TiO2-HS形貌的影响。在以Ti（SO2）：为钛源,尿素为表面活性剂,180℃水热反应15h后得到了微米级、锐钛矿型的TiO2-HS,比表面积和孔容积分别达到了100．728m2／g、0．270cm3／g,平均吸附孔径为10．718nm。将TiO2-HS应用于染料敏化太阳能电池的光阳极,光电转换效率达到5．48％。表明空心球结构提高了材料的比表面积,增强了光子吸收效率,光电性能得到了很大提高。     

Induction of sister chromatid exchanges and micronuclei by titanium dioxide in Chinese hamster ovary-K1 cells

Titanium dioxide (TiO2) has color properties of extreme whiteness and brightness, is relatively inexpensive, and is extensively used as a white pigment in a variety of materials. TiO2, an effective blocker of ultraviolet light, is frequently added to sunscreens and cosmetic creams. However, the genotoxicity of TiO2 remains to be controversial. In this report, we have demonstrated that TiO2 can be transported into Chinese hamster ovary-K1 (CHO-K1) cells. The effects of TiO2 on induction of sister chromatid exchanges (SCE) and micronuclei (MN) were then studied in these cells. The SCE frequency in CHO-K1 cells treated with TiO2 at a nonlethal dose range (0 to 5 microM) for 24 h was significantly and dose-dependently increased. By the conventional MN assay, TiO2 at the dose ranged from 0 to 20 microM slightly increased the MN frequency in CHO-K1 cells. However, in the cytokinesis-block MN assay, the number of MN per 1000 binucleated cells was significantly and dose-dependently enhanced in CHO-K1 cells treated TiO2 at the same dose range for 24 h. These results suggest that TiO2 is a potential genotoxic agent.     

Band gap calculation and photo catalytic activity of rare earths doped rutile TiO2

The density of states (DOS) of 17 kinds of rare earths (RE) doped futile TiO2 was by using fast-principles density functional the-ory (DFF) calculation. The band gap widths of RE doped rutile TiO2 were important factors for altering their absorbing wavelengths. The results show that RE ions could obviously reduce the band gap widths and form of energy of rutile TiO2 except Lu, Y, Yb and Sc, and the order of absorbing wavelengths of RE doped rutile TiO2 were the same as that of the results of calculation. The ratio of RE dopant was an-other important factor for the photo catalytic activity of RE doped rutile TiO2, and there was an optimal ratio of dopant. There was a constant for predigesting the calculation difficulty, respectively, which were 0.5mol.% and 100 mol-1 under supposition. The band gap widths of RE doped rutile TiO2 by DFT calculation were much larger than that by experiment. Finally, by transferring the calculation values to experiment values, it could be found and predicted that RE enlarged obviously the absorbing wavelengh of futile TiO2. In addition, the degree of RE ions edging out the Ti atom using the parameters of RE elements was computed.