Photocatalysis Activity and Physicochemical Structure of Titanium Dioxide Co-doped withN and B

Titanium dioxide co-doped with N and B was prepared by sol-gel method. The photocatalytic activity was evaluated by the photodegradation of methylene blue under visible light. Its physicochemical properties were characterized by means of UV-Vis DRS, XRD, PT-IR, and XPS. The results indicated that N-B-TiO2 has good activity to the photodegradation of MB. Its decolourizing rate of methylene blue solution goes up to 98.4% under the visible light irradiation with 5 h. The doping nitrogen forms N-Ti-O and boron primarily existing in oxide appears in the N-B-TiO2 sample. They response for visible light of TiOa was also exploited.     

TiO2纳米粒子的光催化活性与光伏响应特性研究

TiO2纳米粒子由于其具有良好的化学稳定性、耐光腐蚀性、宽带隙能和大的比表面积等特点而被广泛地应用到光催化降解有机污染物^[1,2]和光催化储能等方面。由于研究手段和研究方法的限制,详细了解催化剂表面光生电荷行为、光谱谱带与催化活性的关系比较困难,而这些关系将为制备高催化活性的光催化剂提供理论基础,由于光催化活性的高低与催化剂的表面性质直接相关,表面光电压谱（SPS）是研究固体材料表面物性和界面间电荷转移过程的有利手段^[3],其为控制光催化机理提供了新的手段。本文利用表面光电压谱方法对系纳米TiO2光催化剂进行了光伏响应测试,发现TiO2的晶型、粒径及表面吸附物对其光催化活性有很大影响。不同性质的表面吸附物可使催化剂表面呈现不同的导电特性,而使其光催化活性不同。利用能带理论和场效应原理对此进行了 合理的解释。     

TiO2/ACF的制备及光催化降解四氯乙烯性能

以钛酸四丁酯为前驱物,活性炭纤维(ACF)为载体,蔗糖为胶粘剂,采用真空吸附水解的方法制得了TiO₂/ACF催化剂.采用BET、XRD、SEM等手段对其物理化学特性进行表征,以四氯乙烯光降解反应为探针反应,考察了TiO₂/ACF催化剂的光催化降解性能.实验结果表明,采用真空吸附水解法可以将TiO₂很好地负载到活性炭纤维表面上.通过优化条件制备的TiO₂/ACF催化剂在光照2h条件下,可以将水中溶解量的四氯乙烯降解90%以上.催化剂可以多次循环使用,光催化反应活性不变.     

Optimizing the photocatalytic properties of hydrothermal TiO2 by the control of phase composition and particle morphology. a systematic approach

The possibility of controlling the photocatalytic activity of TiO2 nanoparticles by tailoring their crystalline structure and morphology is a current topic of great interest. In this study, a broad variety of well-faceted particles with different phase compositions, sizes, and shapes have been obtained from concentrated TiOCl2 solutions by systematically changing temperature, pH, and duration of the hydrothermal treatment. The guide to select the suitable experimental conditions was provided by thermodynamic modeling based on available thermochemical data. By combining the results of TEM, HRTEM, XRD, density, and specific surface area measurements, a complete structural and morphological characterization of the particles was performed. Correlation between the photocatalytic activity in the UV photodegradation of phenol solutions and the particle size was established. Prismatic rutile particles with length/width ratio around 5 and breadth of 60-100 nm showed the highest activity. The surface chemistry of the particles was also investigated. Treatments that decrease the surface acidity, such as washing the powders with ammonia solution and/or calcining at 400 degrees C, have detrimental effect on photocatalytic activity. The overall results suggest correlation between particle morphology and photocatalytic activity and indicate that both electron-hole recombination and adsorption at the surface can be rate-controlling processes. The systematic approach presented in this study demonstrates that a substantial improvement of the photocatalytic activity of TiO2 can be achieved by a careful design of the particle morphology and the control of the surface chemistry.     

TiO2/LaFeO3微纳米纤维的可控制备及光催化性能简

利用静电纺丝技术及水热合成法制备了TiO2/LaFeO3异质结构. 采用场发射扫描电子显微镜(FE-SEM),X射线衍射(XRD),傅里叶变换红外(FTIR)光谱和紫外-可见漫反射光谱(UV-Vis)等手段对TiO2/LaFeO3微纳米纤维的结构和表面形态进行表征. 通过亚甲基蓝(MB)光降解反应研究了其光催化性能. 结果表明,不完全碳化TiO2纤维表面的缺陷位点是LaFeO3纳米粒子的有利生长点. TiO2/LaFeO3异质结材料的带隙明显窄于TiO2,光催化活性得到提高;经140 min紫外光照射后,TiO2/LaFeO3异质结催化剂对MB的降解率为65.34%,分析和探讨了其光催化机理.     

TiO2光催化降解胸腺嘧啶的动力学和机理

考察了用于降解来自嘧啶家族的一种核酸—胸腺嘧啶(C5H6N2O2)的高级氧化过程。结果发现,在光催化剂TiO2作用下,胸腺嘧啶的光降解进行得很快,且在紫外光照射和水溶液中时更为明显。研究了胸腺嘧啶在TiO2催化剂上的吸附、降解动力学、以及pH值对光催化降解胸腺嘧啶性能的影响。另外,考察了胸腺嘧啶降解产物的矿化;比较和讨论了在光催化过程中胸腺嘧啶的消失和矿化速率。同时还研究了氮的矿化,确立了中间产物的识别方法。最后,采用电子密度计算提出了在紫外光照射下TiO2催化剂上胸腺嘧啶降解的可能化学途径。     

TiO2薄膜的吸附能力对罗丹明B光降解过程的影响

采用浸涂的方法在玻璃表面制备了ＴｉＯ２薄膜。Ｘ射线衍射和Ｒａｍａｎ光谱结果表明,薄膜全部由脱钛矿组成。通过罗丹明Ｂ的光降解实验考察了薄膜的催化活性,结果表明,薄膜的吸附性与罗丹明Ｂ的降解途径有很大的影响。     

Photocatalytic activity of a hierarchically macro/mesoporous titania

Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules.     

Relationship Between Photocatalytic Activity and Structure of TiO2 Thin Film

TiO2 thin films with different crystalline structures were prepared by the CVD method. The relationship between photocatalytic activity of a TiO2 thin film and its crystalline type was investigated. These films were characterized by XRD and AFM. Their photocatalytic properties were tested by the degradation of NO2-. The results showed that the crystalline structures of TiO2 thin films are primary anatase and/or rutile when the preparation temperatures were less than 573 K and higher than 773 K respectively. When the preparation temperature was around 623 K, the structures of TiO2 thin films were mixed crystalline structure, which showed the highest catalytic activity. When the ratio of rutile to anatase in TiO2 thin films fell between 0.5 and 0.7, the highest catalytic activity for the degradation of NO2- was found.     

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.     

真空离子溅射法制备TiO2∶Au复合纳米纤维新型光催化剂及其 降解乙醛性能研究

采用静电纺丝技术与真空离子溅射相结合的方法制备了TiO2∶Au复合纳米纤维, 并采用SEM和X射线电子能谱仪对其进行了表征. 结果表明TiO2∶Au纳米纤维的表面形态能通过Au沉积时间得到很好的控制. 同时在紫外光照射下采用乙醛体系考察了TiO2纳米纤维和TiO2∶Au复合纳米纤维催化剂降解乙醛性能, 结果证明TiO2∶Au复合纳米纤维具有更好的催化效率, 紫外光照射70 min后乙醛被完全降解.     

SiO2-TiO2中空型界面光催化剂的制备及性能

采用十八烷基三乙氧基硅烷对TiO2和核壳中空型纳米粒子SiO2-TiO2进行了壳表面疏水烷基化修饰,制备出新型界面光催化剂,并用IR和XRD进行表征.在紫外光照射下,考察了两种界面光催化剂的光稳定性,并以弱酸性黄G溶液的界面光降解为模型反应,考察了催化剂的光催化活性.结果表明,长链烷基成功接枝在了两种纳米粒子表面,且改性前后晶型无变化.与TiO2界面光催化剂相比,SiO2-TiO2界面光催化剂不仅具有优异的界面光稳定性,同时在无搅拌状态下对弱酸性黄G溶液也有良好的光催化活性.     

NH3处理温度对N掺杂P25-TiO2的可见光催化活性的影响

研究了NH3处理温度对N掺杂P25-TiO2可见光催化活性的影响以及可见光催化活性与表面组成和结构的关系．实验结果表明：NH3处理温度在600℃时,有最高活性;在700℃,P25-TiO2转变为以金红石相为主,表面未发生N掺杂,这与700℃时NH3分解有关;N掺杂浓度、可见光吸收两者与可见光催化活性之间均不存在顺变关系．讨论揭示：N掺杂P25-TiO2的可见光催化活性是由三个要素协同作用产生：（i）表面生成大量束缚单电子氧空位（Vo）,（ii）表面有N掺入,（iii）晶型以锐态矿为主,三者缺一不可．     

过渡金属掺杂和碳纳米管（CNT）接枝双重改性TiO2光催化剂

提出了一种过渡金属掺杂和碳纳米管(CNT)双重改性TiO2的新方法:首先采用溶胶-凝胶法合成掺杂镍和铁的二氧化钛基催化剂,然后采用流化床化学气相沉积方法(FBCVD)在二氧化钛基催化剂表面接枝生长CNT,得到CNT/Fe-Ni/TiO2复合光催化剂.通过X射线衍射、扫描电子显微镜、比表面分析、拉曼光谱、紫外-可见吸收光谱、荧光光谱等方法考察了双重改性复合光催化剂CNT/Fe-Ni/TiO2的结构和性能,通过降解亚甲基蓝溶液评价了双重改性复合光催化剂的活性.结果表明,在TiO2表面接枝的CNT具有较好的石墨化结构,CNT生长过程中小部分TiO2由锐钛矿向金红石晶型转变.过渡金属和CNT双重改性有效地克服了TiO2的比表面积小、量子效率低等缺点,明显提高了TiO2的光催化活性.     

Effect of titanium dioxide on photostability of solid-state mequitazine

TiO(2) has been widely used in pharmaceutical products, and it also has been used as a photocatalyst. In this study, the influence of photocatalytic activity on the stability of solid-state mequitazine, an H(1)-blocker, was investigated. The photo-degradation of mequitazine with TiO(2) occurred under irradiation with both light sources. The degree of degradation of mequitazine with anatase was higher than that of rutile. The degradation was significantly enhanced with increasing relative humidity. The relationship between the apparent degradation rate constant and water vapor pressure could be clearly described by a simple power law. The major photo-degradation products of mequitazine, resulting from photocatalytic activity of TiO(2), were mequitazine-S-oxide and mequitazine-sulphone. A remarkable degradation of mequitadine occurred with addition of TiO(2), and its photocatalytic activity was controlled by water vapor pressure. The photo-degradation of mequitazine with TiO(2) is a different process from mequitazine without TiO(2), because mequitazine-S-oxide and mequitazine-sulphone are not formed with normal photo-degradation of mequitazine.     

二氧化钛光催化产生超氧自由基的形态分布研究

超氧阴离子自由基(O·-2)是TiO2光催化反应过程中产生的重要活性氧物种.本研究使用硝基四氮唑蓝(NBT)作为超氧自由基捕获剂,将其与TiO2混合后光照,研究TiO2光反应过程中产生的总O·-2;然后采用连续流动-分光光度法,将TiO2光照后,再与NBT混合,研究TiO2光反应过程中表面吸附的O·-2.在此基础上,研究了3种不同晶相TiO2(锐钛矿、金红石、P25)光催化反应中生成的总O·-2和表面吸附的O·-2.结果表明,3种不同晶相TiO2的总O·-2生成量依次为P25>锐钛矿>金红石;而表面吸附的O·-2的生成量相差不大,锐钛矿表面吸附O·-2略高.不同于以往仅对光催化反应中总活性氧(ROS)检测,本研究同时还对吸附在颗粒物表面ROS的产生和分布进行研究,有助于加深光催化污染物降解和微生物消毒作用机制的认识和理解.     

Use of titanium dioxide photocatalysis on the remediation of model textile wastewaters containing azo dyes

The photocatalytic degradation of two commercial textile azo dyes, namely C.I Reactive Black 5 and C.I Reactive Red 239, has been studied. TiO(2) P25 Degussa was used as catalyst and photodegradation was carried out in aqueous solution under artificial irradiation with a 125 W mercury vapor lamp. The effects of the amount of TiO(2) used, UV-light irradiation time, pH of the solution under treatment, initial concentration of the azo dye and addition of different concentrations of hydrogen peroxide were investigated. The effect of the simultaneous photodegradation of the two azo dyes was also investigated and we observed that the degradation rates achieved in mono and bi-component systems were identical. The repeatability of photocatalytic activity of the photocatalyst was also tested. After five cycles of TiO(2) reuse the rate of colour lost was still 77% of the initial rate. The degradation was followed monitoring the change of azo dye concentration by UV-Vis spectroscopy. Results show that the use of an efficient photocatalyst and the adequate selection of optimal operational parameters may easily lead to a complete decolorization of the aqueous solutions of both azo dyes.     

Photocatalytic degradation of methyl orange over metalloporphyrins supported on TiO2 Degussa P25

The photocatalytic activity of meso-tetraphenylporphyrins with different metal centers (Fe, Co, Mn and Cu) adsorbed on TiO(2) (Degussa P25) surface has been investigated by carrying out the photodegradation of methyl orange (MO) under visible and ultraviolet light irradiation. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV (DRS-UV-vis) and infrared spectra. Copper porphyrin-sensitized TiO(2) photocatalyst (CuP-TiO(2)) showed excellent activity for the photodegradation of MO whether under visible or ultraviolet light irradiation. Natural Bond Orbital (NBO) charges analysis showed that methyl orange ion is adsorbed easier by CuP-TiO(2) catalyst due to the increase of induced interactions.     

铝基板的界面扩散对薄膜型TiO2光催化活性的影响

以钛酸四丁酯为前驱体, 采用溶胶-凝胶法在铝基板表面制备了纳米晶TiO2薄膜. 运用XRD、SEM和XPS对制得的薄膜进行表征, 并测试了薄膜光催化降解亚甲基蓝(MB)的活性. 结果表明, TiO2薄膜样品在450 ℃焙烧30 min后, 晶粒排列比较致密, 粒径为10-20 nm, 并与铝基板紧密结合; 薄膜与铝基板发生了明显的界面扩散, 薄膜中的Al元素来自铝基板的界面扩散, 且界面层很宽, 扩散层厚度约为75 nm; 界面扩散的发生直接导致了TiO2薄膜的光催化活性下降. 但随着薄膜厚度增加, 铝基板对TiO2薄膜降解亚甲基蓝催化活性的影响不断减小.     

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."