Beta zeolite supported sol-gel TiO2 materials for gas phase photocatalytic applications

Beta zeolite supported sol-gel TiO(2) photocatalytic materials were prepared according to a sol-gel route in which high specific surface area Beta zeolite powder was incorporated into the titanium isopropoxide sol during the course of the sol-gel process. This led to an intimate contact between the zeolite surface and the TiO(2) precursors, and resulted in the anchorage of large amounts of dispersed TiO(2) nanoparticles and in the stabilization of TiO(2) in its anatase form, even for high TiO(2) wt. contents and high calcination temperatures. Taking the UV-A photocatalytic oxidation of methanol as gas phase target reaction, high methanol conversions were obtained on the Beta zeolite supported TiO(2) photocatalysts when compared to bulk sol-gel TiO(2), despite lower amounts of TiO(2) within the photoactive materials. The methanol conversion was optimum for about 40 wt.% TiO(2) loading and calcination temperatures of 500-600°C.     

Deactivation mechanism of PtOx/TiO(2) photocatalyst towards the oxidation of NO in gas phase

This study has been undertaken to investigate the roles of PtO and PtO(2) deposits in photocatalytic oxidation of NO over Pt-modified TiO(2) catalysts. These photocatalysts were prepared by neutralization method and characterized by XRD, BET, XPS, TEM and FTIR. It was found that Pt dopant existed as PtO and PtO(2) particles in as-prepared photocatalysts. And these Pt dopants would change their oxidation states during the photocatalytic oxidation reaction. An in situ XPS study indicated that a portion of PtO(2) on the surface of Pt/TiO(2) was reduced to PtO under UV irradiation. The migration of electrons to PtO(2) particles could separate the electrons and holes, resulting in the improvement of photocatalytic activity. And the depletion of PtO(2) by electrons could lead to the deactivation of Pt/TiO(2) catalyst. Moreover, PtO particles could be corroded to form Pt(2+) ions by HNO(3), which was one of the products of photocatalytic oxidation of NO. NO would adsorb on Pt(2+) related sites to form Pt(n+)-NO nitrosyls, retarding photocatalytic oxidation of NO to NO(2).     

Oxidation of gas phase trichloroethylene and toluene using composite sol-gel TiO2 photocatalytic coatings

The previously developed composite sol-gel (CSG) process is proposed for the deposition of thick (10-50 microm) porous films of photocatalytic TiO2. The CSG titania was developed by binding pre-calcined TiO2 particles with TiO2 sol. It had relatively high surface area (15-35 m2/g) and good resistance against mechanical stress and abrasion. Photocatalytic activity tests were carried out on trichloroethylene (TCE) and toluene, and compared with those of standard Degussa P-25 titania. The CSG photocatalyst provided good photo-efficiency in removing both pollutants from contaminated air streams. When compared with P-25 titania, the CSG photocatalyst showed a similar photo-efficiency with first-order kinetic rate constants not significantly different from that of P-25. For both photocatalysts the rate of photocatalytic oxidation of TCE was significantly greater than that obtained for toluene. Overall, the combination of better mechanical integrity, resistance against abrasion, and comparable photocatalytic efficiency of the CSG titania versus that of P-25 titania, make the composite sol-gel (CSG) photocatalyst a viable alternative for industrial applications where long term stability, superior mechanical properties, and good photo-efficiency are of critical value.     

TiO2 hydrosols with high activity for photocatalytic degradation of formaldehyde in a gaseous phase

Two types of TiO2 hydrosols (TOSO and HTO) were prepared from titanium sulfate (TiOSO4) and metatitanic acid (H2TiO3) by a chemical precipitation-peptization method, respectively. The prepared hydrosols were characterized by means of X-ray diffraction, particle size distribution, scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller and Barret-Joyner-Halender methods. The results showed that the TiO2 hydrosols with an anatase crystal structure had smaller particle sizes, higher surface areas, larger pore volume, and higher transparence than Degussa P-25 suspension. The photocatalytic activity of the TiO2 hydrosols was evaluated for formaldehyde degradation under UVA illumination in a gaseous phase. The results demonstrated that the photocatalytic activity with the catalyst loading of 2mgcm(-2) was ranked as an order of HTO>TOSO>P-25. The photocatalytic activity was further studied using the HTO catalyst under different experimental conditions. The results showed that catalyst loading, relative humidity, and initial concentration could influence the efficiency of HCHO photocatalytic degradation. It was found that a catalyst loading of more than 2mgcm(-2) and a relative humidity of 55% were two essential conditions for achieving the best performance under these experimental conditions. The repeated experiments indicated that the HTO catalyst was reasonably stable and could be repeatedly used for the HCHO oxidation under UVA irradiation. This investigation would be helpful to promote the application of TiO2 photocatalytic technique for indoor air purification.     

Sonochemical synthesis and photocatalytic activity of meso- and macro-porous TiO(2) for oxidation of toluene

Meso-and macro-porous TiO(2) were synthesized by ultrasonic induced solvothermal method. Octadecylamine as a soft template was used to direct the formation of porous structure. The as-prepared porous TiO(2) was characterized by low angle and wide angle X-ray diffraction, N(2) adsorption-desorption isotherms and BET surface area. The energy influence of ultrasound and heat and concentration of nitric acid for post extraction on formation of porous structure were investigated. The photocatalytic activities of TiO(2) were investigated by degrading toluene gas under UV light. The results revealed that proper energy facilitates the formation of porous structure and too low concentration of nitric acid cannot extract template from pores. The photocatalytic activities of TiO(2) with porous structure are higher than those of nonporous ones.     

银掺杂TiO2光催化剂的制备及光催化性能研究

采用溶胶-凝胶法,以钛酸四丁酯、硝酸银为原料制备了不同银含量掺杂TiO2光催化剂,并以TG-DTA、XRD、TEM对样品进行了表征,XRD结果显示,掺杂银TiO2光催化剂为锐钛矿型,银掺杂量较低时,银均匀分布在TiO2的表面,在掺杂量为4%时,出现银的团聚。光催化亚甲基蓝结果表明,银掺杂TiO2光催化剂比未掺杂TiO2降解率明显提高,在2%银掺杂TiO2光催化剂用量为25mg,pH值为6～8,降解时间为120min,降解率可达93%。     

微乳液法制备纳米二氧化钛及其光催化活性

以TiCl4为原料，在CTAB／正丁醇／环己烷／水组成的微乳液体系中合成了纳米TiO2。采用TG-DTA、XRD和TEM等分析手段对粉体的粒径、物相、形貌和热稳定性进行了表征．通过粉体对罗丹明B的降解情况对其光催化活性进行了测试。结果表明材料具有良好的光催化氧化性能。     

钼氮共掺杂TiO2的制备及其光催化活性

采用简单的溶胶-凝胶法制备了一系列不同钼掺杂比例的钼氮共掺杂TiO2光催化剂,并通过X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis DRSs)及光致发光光谱(PL)等手段对催化剂进行了表征,并通过降解亚甲基蓝(MB)对催化剂光催化活性进行了评价.结果发现,掺杂后TiO2在可见光区吸收...     

Effects of ZrO2 addition on phase stability and photocatalytic activity of ZrO2/TiO2 nanoparticles

ZrO₂/TiO₂ nanoparticles with various Zr/Ti ratios (0–0.9) were prepared by a polymer complex solution method (PCSM). The prepared samples were characterized using transmission electron microscopy (TEM), the Brunauer, Emmett & Teller (BET) method, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The ZrO₂/TiO₂ photocatalyst showed a high specific area and small crystal size. The XRD pattern for the Zr/Ti = 0.1 sample indicated that the addition of ZrO₂ stabilized the anatase phase of TiO₂ up to 800 °C. The photocatalytic activity of Zr/Ti = 0.1 sample was higher than that of the TiO₂ sample and commercially available Degussa P25. The high photocatalytic activity can be attributed to stronger adsorption in the visible light region, higher specific area, smaller crystal size and increased surface OH groups.     

多孔TiO2的制备表征及光催化研究

以钛酸四丁酯为前驱物，在溶胶-凝胶法和硬脂酸法的合成样品的过程中添加正硅酸乙酯，分别合成出纳米TiO2，焙烧成晶后通过HF除去硅，形成了多孔TiO2。通过XRD、SEM、UV-Vis、BET等测试手段，比较正硅酸乙酯对不同合成方法合成的样品的影响。在对甲基橙的紫外光催化试验中，添加正硅酸乙酯再由HF处理后合成的样品表现出较高的催化活性，这与此方法合成的样品的表面积较大有关。     

Preparation and photocatalytic activity of nanoglued Sn-doped TiO2

In this paper, Sn-doped TiO(2) photocatalyst was prepared and immobilized on a glass substrate using an about-to-gel SiO(2) sol as a nanoglue. The characterization of the Sn-doped TiO(2) by XRD showed that 5% Sn content is formed by anatase and rutile crystallites. Characterization of the nanoglued photocatalyst by the BET measurement, TEM, and SEM showed that the photocatalyst was a nanoporous material with a high-surface area. The Sn-doped TiO(2) was uniformly dispersed within the three-dimensional network of the silica in the form of nanoparticles. The nanoglued photocatalyst showed high photocatalytic activity during the degradation of penicillin under UV light. The effect of different Sn content on the amount of hydroxyl radical was discussed by using salicylic acid as probe molecules. The results show that an appropriate amount of Sn dopant can greatly increase the amount of hydroxyl radicals generated by TiO(2) nanoparticles, which are responsible for the obvious increase of photocatalytic activity.     

Influence of structure parameters and crystalline phase on the photocatalytic activity of TiO2 nanotube arrays

Titanium oxide nanotube arrays (TiO2-NTAs) with different diameters and lengths are prepared by anodization of titanium foils in a water/ethylene glycol solution (5:95 V/V) containing 0.3 wt% NH4F. The effects of the diameters, lengths and crystalline phases of the NTAs on the photocatalytic (PC) activity are systematically evaluated. Larger pore diameter results in higher PC activity. The PC activity increases initially and then decreases with lengths for TiO2-NTAs and the optimal length that yields the highest PC activity is observed to be 6.2 microm. The crystalline phase and corresponding PC activity depend on the calcination temperature and their relationship is also investigated. The amorphous-to-anatase and anatase-to-rutile phase transitions initially occur at 300 and 500 degrees C, respectively. The PC activity of TiO2-NTAs initially increases with calcination temperature from 250 to 500 degrees C and then decreases at higher calcination temperature. The enhanced PC activity observed from the samples annealed at 250-450 degrees C is attributed to the better anatase crystalline structure at higher calcination temperature. The highest PC activity with regard to photodecomposition of methyl orange is observed from TiO2-NTAs calcined at 500 degrees C, which coincides with the anatse-to-rutile phase transformation. The synergistic effect of the anatase TiO2-NTAs and rutile barrier layers facilitate interfacial electron transfer consequently enhancing the PC activity. Further elevation of the calcination temperatures to 550 and 600 degrees C exhibits diminished PC activity because the NTs become shorter due to conversion of the bottom of anatase NTs into rutile film.     

Improved photocatalytic activity of zeolite- and silica-incorporated TiO2 film

Porous TiO2 film was prepared by sol-gel method from TiO2 sol containing polyvinylpyrolidone (PVP). Photocatalytic activity of the film was evaluated by the elimination rate of ethylene. Several adsorbents including zeolite and silica powders were incorporated into the TiO2 film. All the adsorbents enhanced the activity. The optimum adsorbent content was 0.005-0.01 g/ml of the coating sol solution. Silica provided better activity than zeolite. At high humidity and in dry air the activity decreased.     

钛酸酯前驱体制备纳米TiO2块体的研究

以四氯化钛、甘油与六次甲基四胺为原料发泡制得钛酸酯发泡前驱物,后者经高温热分解制得了纳米TiO2 块体;使用FT IR、TG DTA、XRD、SEM等对发泡前驱物和纳米 TiO2 块体进行了表征并初步考察了纳米TiO2 块体的光催化活性。结果表明:钛酸酯发泡前驱物在 450℃马弗炉中焙烧 2. 0h 得 TiO2 块体,为纯锐钛矿相纳米结构,块体由 200nm 左右的二级粒子堆积构成,二级粒子由粒径为 16nm 左右的基本粒子构成;550℃以后所得 TiO2 块体含不同比例的金红石相;纯锐钛矿相纳米结构块体具有较高的光催化活性,且易于沉降或过滤回收。     

Hydrothermal synthesis and photocatalytic activity of anatase TiO2 nanofiber

TiO2 nanofiber consisting of 15 +/- 5 nm anatase grains was synthesized by hydrothermal treatment of fibrous hydrogen titanate precursor at 180 degrees C for 20 h. The hydrogen titanate precursor was synthesized by hydrothermal treatment of commercial P25 TiO2 powder in 10 M NaOH at 200 degrees C for 20 h followed by soaking in 0.1 M HNO3 to perform ion exchange between the as-synthesized Na titanate and H. By controlling pH of the solution during hydrothermal treatment of the hydrogen titanate precursor, pure anatase TiO2 nanofiber was obtained. Its band-gap energy determined from the onset of diffused reflectance spectrum was 3.19 eV which is equal to that of anatase TiO2 powder. The TiO2 nanofiber showed higher photodecomposition efficiency than the Cotiox KA-100 TiO2 but lower than the P25 TiO2. Photodegradation is the predominant process for 'Reactive blue 171' removal.     

TiO_2-海藻酸钙复合膜的表征、对染料的光催化降解及TiO_2回收

为了解决TiO2纳米粒子难分离,负载的催化剂难回收等问题,首先,将TiO2与海藻酸钠充分混合制成铸膜液,在玻璃板上刮膜,经钙离子交联制备了TiO2-海藻酸钙(T-CA)复合膜。然后,对T-CA复合膜进行了SEM和XRD表征,并研究了T-CA复合膜对染料的光催化降解性能。最后,将T-CA复合膜从染料降解液中取出,浸泡在柠檬酸钠水溶液中,柠檬酸根对钙离子的结合力较强,可使海藻酸盐水凝胶溶解,离心分离TiO2纳米粒子并清洗干燥后,得到了回收TiO2;利用SEM、TEM、FTIR和XRD对回收TiO2进行了表征。结果表明:T-CA复合膜对甲基橙的光催化降解率可达82.37%。回收TiO2与初始的TiO2几乎完全一样,可重新使用且催化能力不变。该方法是一种绿色环保、方便快速的从载体中回收TiO2纳米粒子的方法。     

不同酸催化剂对有机-钛柱撑蒙脱石复合材料光催化活性的影响

以钛酸丁酯为前驱体,分别采用醋酸和盐酸为溶胶-凝胶法制备TiO2溶胶的酸催化剂,将制备的溶胶分别加入经阳离子表面活性剂十六烷基三甲基溴化铵改性的浙江临安和内蒙古膨润土中,制备了有机-钛柱撑膨润土复合光催化剂,并对其进行XRD,SEM,BET表征.实验结果表明:钛阳离子经交换进入了膨润土层间,并以锐钛矿型的晶形存在,而且制备的复合光催化剂具有较好的层状结构,其比表面积均比相应的未经柱撑的膨润土的比表面积大.并且以甲基橙为目标污染物,考察了所制备的有机-钛柱撑膨润土复合光催化剂的吸附性能和光催化活性,发现两种方法所制备的复合光催化剂均具有较好的光催化活性.但是由于在醋酸介质中溶胶的水解速度较慢,可形成稳定均质的凝胶,因而形成的TiO2粒径相对较小,因此对于不同类型的膨润土,以醋酸为酸催化剂制备的复合光催化剂均比用盐酸为酸催化剂制备的复合光催化剂的催化活性好.