Photocatalytic performance of Sn-doped TiO2 nanostructured mono and double layer thin films for Malachite Green dye degradation under UV and vis-lights

Nanostructure Sn(4+)-doped TiO(2) based mono and double layer thin films, contain 50% solid ratio of TiO(2) in coating have been prepared on glass surfaces by spin-coating technique. Their photocatalytic performances were tested for degradation of Malachite Green dye in solution under UV and vis irradiation. Sn(4+)-doped nano-TiO(2) particle a doping ratio of about 5[Sn(4+)/Ti(OBu(n))(4); mol/mol%] has been synthesized by hydrotermal process at 225 degrees C. The structure, surface and optical properties of the thin films and/or the particles have been investigated by XRD, BET and UV/vis/NIR techniques. The results showed that the double layer coated glass surfaces have a very high photocatalytic performance than the other one under UV and vis lights. The results also proved that the hydrothermally synthesized nano-TiO(2) particles are fully anatase crystalline form and are easily dispersed in water. The results also reveal that the coated surfaces have hydrophilic property.     

Preparation of re-usable photocatalytic filter for degradation of Malachite Green dye under UV and vis-irradiation

Sn(4+) doped and undoped nano-TiO(2) particles easily dispersed in water were synthesized without using organic solvent by hydrothermal process. Nanostructure-TiO(2) based thin films were prepared on flyswatter substrate, made with stainless steel, by dip-coating technique. The structure, surface and optical properties of the particles and thin films were characterized by element analysis and XRD, BET, SEM and UV/vis/NIR techniques. The photocatalytic performance of the films were tested for degradation of Malachite Green dye in solution under UV and vis-lights. The results showed that the coated flyswatter has a very high photocatalytic performance for the photodegradation of Malachite Green irradiated with UV and vis-lights. The results also proved that the hydrothermally synthesized nano-TiO(2) particles are fully anatase crystalline form and are easily dispersed in water, the coated surfaces are hydrophilic, and the doping of transition metal ion efficiently improved the degradation performance of TiO(2)-coated flyswatter. The photocatalytic performances determined at both irradiation conditions were very good and were almost similar to each other for Sn(4+) doped TiO(2)-coated flyswatter and it can be repeatedly used with increasing photocatalytic activity compared to undoped TiO(2)-coated flyswatter.     

Photocatalytic antibacterial performance of Sn(4+)-doped TiO(2) thin films on glass substrate

Pure anatase, nanosized and Sn(4+) ion doped titanium dioxide (TiO(2)) particulates (TiO(2)-Sn(4+)) were synthesized by hydrothermal process. TiO(2)-Sn(4+) was used to coat glass surfaces to investigate the photocatalytic antibacterial effect of Sn(4+) doping to TiO(2) against gram negative Escherichia coli (E. coli) and gram positive Staphylococcus aureus (S. aureus). Relationship between solid ratio of TiO(2)-Sn(4+) in coatings and antibacterial activity was reported. The particulates and the films were characterized using particle size analyzer, zeta potential analyzer, Brunauer-Emmett-Teller (BET), X-ray diffractometer (XRD), SEM, AAS and UV/VIS/NIR techniques. The results showed that TiO(2)-Sn(4+) is fully anatase crystalline form and easily dispersed in water. Increasing the solid ratio of TiO(2)-Sn(4+) from 10 to 50% in the coating solution increased antibacterial effect.     

SnP2+-TiO2的可见光催化活性及其在介孔蒙脱石上的负载

分别以氯化锡和氯化亚锡为Sn源,使用溶胶-凝胶法制备出不同掺杂量的Sn-TiO2,比较了Sn2+与Sn4+对掺杂后TiO2可见光催化活性的影响.实验结果显示,Sn2+与Sn4+均能显著抑制TiO2晶粒生长,并促进其晶型转变.但Sn2+-TiO2的可见光催化活性却明显优于Sn4+-TiO2,这主要是Sn2+外层半充满的电子轨道结构引起的.将可见光催化活性很高的Sn2+-TiO2负载于大比表面积、高稳定性的介孔蒙脱石上,由于载体与Sn-TiO2之间发生了相互作用,负载后样品的UV-Vis光谱吸收边相对于Sn-TiO2发生了显著红移,且可见光催化活性也有大幅提高.     

磁性La3+掺杂TiO2的制备及性能

利用溶胶-凝胶法,在室温条件下,以钛酸四丁酯、硝酸镧为主要原料,无水乙醇为溶剂,冰醋酸为抑制剂,浓硝酸为催化剂制得稳定的掺La3+TiO2溶胶,陈化后的凝胶经不同温度煅烧3h后制得不同掺La3+量的TiO2。通过XRD对不同煅烧温度及不同掺La3+量的TiO2进行了表征;以紫外光为光源,研究了掺La3+-TiO2对甲基橙溶液的光降解效果。用化学共沉淀法制备了具有强磁性的Fe3O4水基磁流体,再与La3+掺杂TiO2进行复合,制备了Fe3O4负载量不同的磁性La3+掺杂TiO2,研究了Fe3O4负载量不同的La3+掺杂TiO2对甲基橙的光催化降解效果、磁分离回收率的影响。结果表明,掺La3+量及煅烧温度对TiO2的晶型、各晶型TiO2的相对含量及对甲基橙的光降解效果均有影响。La3+掺杂TiO2比纯TiO2显示出更强的光催化性能,掺La3+量2%,热处理温度450℃的La3+掺杂TiO2光催化活性最高。Fe3O4负载量为10%的Fe3O4/La3+-TiO2对甲基橙的降解率8h时为99.4%;磁分离回收率达97.39%。     

添加磷酸根对纳米二氧化钛晶相的控制

以TiCl4为前驱体添加磷酸盐通过水热法制备了纳米TiO2。通过X射线衍射仪、差热分析仪、扫描电子显微镜、比表面仪(BET)和光化学反应器等手段对所制备的TiO2的颗粒晶型、失重、形貌、比表面和降解罗丹明B的能力进行了表征。结果表明,随着磷酸根的添加,TiCl4水解生成的TiO2的晶型由纯金红石型向锐钛矿型转换,且所合成的锐钛矿和金红石的混晶样品的光催化活性明显高于单独晶相的光催化活性。     

Photoinduced hydroxyl radical and photocatalytic activity of samarium-doped TiO(2) nanocrystalline

Sm(3+)-doped TiO(2) nanocrystalline has been prepared by sol-gel auto-combustion technique and characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, and also UV-vis diffuse reflectance spectroscopy (DRS). These Sm(3+)-doped TiO(2) samples were tested for methylene blue (MB) decomposition and *OH radical formation. The analysis of *OH radical formation on the sample surface under UV irradiation was performed by fluorescence technique with using terephthalic acid, which readily reacted with *OH radical to produce highly fluorescent product, 2-hydroxyterephthalic acid. It was observed that the presence of Sm(3+) ion as a dopant significantly enhanced the photocatalytic activity for MB degradation under UV light irradiation because both the larger specific surface area and the greater the formation rate of *OH radical were simultaneously obtained for Sm(3+)-doped TiO(2) nanocrystalline. The adsorption experimental demonstrated that Sm(3+)-TiO(2) had a higher MB adsorption capacity than undoped TiO(2) and the adsorption capacity of MB increased with the increase of samarium ion content. The results also indicated that the greater the formation rate of *OH radical was, the higher photocatalytic activity was achieved. In this study, the optimum amount of Sm(3+) doping was 0.5 mol%, at which the recombination of photo-induced electrons and holes could be effectively inhibited, the highest formation rate of *OH radicals was, and thereby the highest photocatalytic activity was achieved.     

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%.     

湿法碳氮硫共掺杂TiO2的制备及其光催化活性

以全硫碳酸铵为掺杂剂,采用湿法由硫酸钛出发制得碳氮硫共掺杂TiO2,通过XRD和XPS对掺杂TiO2进行了表征,并对掺杂TiO2的光催化活性进行了考察。结果表明,微波辅助加热制备的掺杂TiO2中,C元素部分替位取代了TiO2晶格中的Ti 4+;N元素以两种掺杂形式存在,即进入TiO2晶格替位取代O2-产生掺杂和通过化学吸附进入晶格间隙产生掺杂;S元素主要提供S 2p形成S6+取代Ti 4+进入晶格进行掺杂;以甲基橙溶液为对象进行光催化降解,当掺杂量α为1.6、500℃焙烧2h时,掺杂TiO2表现出较高的可见光催化活性,光照70min使浓度为20mg/L的甲基橙溶液的降解率达到99.64%,明显提高了纳米TiO2的光催化活性。     

蝴蝶结状TiO2纳米粒子的制备及其光催化性能研究

以四甲基氢氧化铵（TMAOH）为结构导向剂,钛酸四丁酯（Ti（OBu）4）为钛源,低温水浴处理,再经180℃下水热晶化制备纳米TiO2,采用FT-IR、XRD、TEM、UV—Vis等测试手段对其结构和形貌进行表征,并通过苯酚的光催化降解实验测试其光催化性能,结果表明,TiO2为锐钛矿相,结晶度高,所得TiO2粒子为纳米棒,界面清晰,规整度高,经紫外光照6h后,对苯酚的降解率可达62．3％,具有较高的光催化活性。     

(N, F)-codoped TiO2 Nanocrystals as Visible Light-activated Photocatalyst

(N, F)-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The (N, F)-codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.     

Low-temperature preparation and characterization of iron-ion doped titania thin films

Iron-ion doped titania thin films with an anatase phase were successfully synthesized in this study using the high-pressure crystallization (HPC) process. The crystallization temperature of Fe(3+)-doped TiO(2) thin films was markedly reduced to be as low as 125 degrees C. The films prepared via the HPC process have a more uniform microstructure and smaller grain sizes than the films prepared via the atmospheric-pressure annealing process. The films prepared via both processes were found to have photocatalytic properties under visible light. The films prepared via the HPC process exhibited enhanced photocatalytic activities in comparison with the films annealed via the conventional process. Increasing the annealing temperature in the HPC process resulted in an improvement in the photocatalytic properties because of an increase in the crystallinity of the prepared films. The HPC process was demonstrated to be a potential method for synthesizing visible-light driven titania thin films with enhanced photocatalytic activities at low temperatures.     

棒状纳米微晶纤维素诱导制备花状TiO2纳米晶体

以棒状纳米微晶纤维素(Nanocrystalline cellulose,NCC)为形貌诱导剂,TiCl4为原料,采用水解法在70℃的温度下反应4～6 h,制备了TiO2花状纳米晶体.采用TEM、HRTEM、XRD和FTIR对不同条件下制得的TiO2晶体的微观形貌、晶粒尺寸和晶相组成进行了表征,探讨了TiCl4的用量及反应时间对晶体形貌和晶型的影响,并对其形成机理进行分析.纳米微晶纤维素表面富含大量羟基,可与TiO2之间形成氢键连接,促使TiO2在其表面的异质成核和生长,同时纳米微晶纤维素在TiO2表面的吸附作用,改变了各晶面的表面能和生长速度,使TiO2沿着[110]方向优先生长形成一维针状物,针状物再进一步聚集形成花状聚集体.以甲基橙为目标污染物,测试了所得TiO2纳米花状晶体的光催化性能.结果表明,随着TiCl4用量的增多及反应时间的延长,所制得的TiO2纳米晶体中金红石含量增多,形貌逐渐复杂化,光催化性能下降.     

Photocatalytic degradation of Direct Red 23 dye using UV/TiO2: Effect of operational parameters

In this study, the photocatalytic degradation of Direct Red 23 (Scarlet F-4BS) was investigated in UV/TiO2 system. The effect of catalyst loading and pH on the reaction rate was ascertained and optimum conditions for maximum degradation were determined. The results obtained showed that acidic pH is proper for the photocatalytic removal of Direct Red 23. In addition, the effects of several cations (Cu2+, Al3+, Cr3+, and Sn4+) and anions (BiO3(-), SO4(2-), and CN(-)) and C2H5OH were examined in this photocatalytic process. On the order hand, three types of catalysts (Fe2O3, SnO2, and ZnO) were compared with TiO2. After 90 min reaction, the relative decomposition order established was UV/TiO2>UV/SnO2>UV/Fe2O3>UV/ZnO.     

二氧化钛光催化剂的制备及其性能研究

本文采用溶胶-凝胶法(sol-gel)制备了纯相和掺杂不同量Fe3+、Zn2+、Cu2+和S2-的TiO2粉体,并讨论了不同热处理温度、掺杂元素及掺杂量对TiO2粉体光催化性能的影响。以甲基橙溶液为目标降解物,用紫外可见分光光度计对TiO2粉体的光催化性能进行测定。实验结果表明,煅烧温度为450℃、掺入0.25%的Zn2+的TiO2粉体的催化效果最好。     

Visible light induced electron transfer process over nitrogen doped TiO(2) nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).     

Cyclic performance and photo-induced crystalline growth of nanostructured AgI/TiO2 visible light photocatalyst

Nanostructured AgI/TiO2 visible light photocatalyst was prepared with AgNO3, KI, and Ti(OBu)4 as precursors. The photocatalyst was used repeatedly to degrade methylene blue and methyl orange in water with visible light irradiation. Though a high photocatalytic efficiency was observed for the photocatalyst in the first cycle, the photocatalytic efficiency was found to decrease dramatically in subsequent cycles. X-ray diffraction and SEM analyses revealed an obvious crystalline growth of AgI in AgI/TiO2 nanocomposite after photocatalysis or visible light irradiation. It was proposed that photo-induced crystalline growth had occurred to AgI in the course of photocatalysis and resulted in dramatic decrease in the photocatalytic efficiency of the photocatalyst. Photo-induced crystalline growth may be a limiting factor for the lifetime of photocatalysts and should be examined as an important aspect of photostability when new photocatalysts are developed.     

二氧化钛纳米棒的制备及其晶体生长机理分析

采用溶剂热法合成具有高结晶性与单分散性的TiO₂纳米棒. 采用TEM、XRD、HRTEM等对样品的微观结构进行表征, 并考察了TiO₂纳米棒对亚甲基蓝的光催化性能. 通过控制反应时间、反应温度, 研究纳米棒的形貌演变规律.结果表明, 可以通过“奥斯特瓦尔德熟化”和“取向接触”两种晶体生长过程制备出棒状TiO₂纳米晶, 降低纳米晶的表面能是晶体生长与形貌演变的主要驱动力; 高结晶性的TiO₂纳米棒具有高于P25的光催化能力.     

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%.     

Pt负载型二氧化钛纳米管/纳米晶复合光催化剂的制备及其光催化性能

结合强吸附能力与高光催化活性的催化剂有望更有效地除去废水中的污染物. 以Degussa P25二氧化钛为原料, 采用水热法制备了二氧化钛纳米管(简称为TNTs), 将TNTs加入到溶有氯铂酸和柠檬酸(还原剂)的无水乙醇中, 在蒸汽相水解装置中通过一步法制备了Pt负载型二氧化钛纳米管/纳米晶复合光催化剂. 蒸汽相处理过程中, 部分纳米管转变为锐钛矿相TiO₂, 仍有部分以管的形式存在, 使纳米复合物保留了较高的吸附能力. 利用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面及孔隙度分析仪等方法对产物进行了表征. 结果表明, 粒径约为4 nm的金属性Pt较好地分散在TNTs及由纳米管转变而来、晶粒尺寸约为8 nm的锐钛矿相TiO₂晶粒表面, 复合物保留了高于216 m²/g的比表面积. 光催化降解染料酸性红及亚甲基蓝的实验结果表明, 纯管有较好的吸附能力, 但是光催化性能非常低, 经120℃蒸气处理并负载贵金属Pt后光催化活性有了显著的提高.