溴代甲烷在TiO2上的光催化降解研究

系统地研究了CH₃Br在溶胶-凝胶法制备的TiO₂催化剂上的气相光催化氧化行为,考察了催化剂煅烧温度、催化剂中残留NO-3、反应物料中的水份、反应温度等催化剂制备及反应条件对催化剂反应性能的影响,并结合XRD、BET比表面积和FTIR等表征结果对TiO₂催化剂的反应行为进行了解释.实验结果表明,CH₃Br在TiO₂上的气相光催化氧化是典型的一级反应,表观活化能为13.7kJ/mol.反应初始阶段存在显著的催化剂失活现象,催化剂高温煅烧,NO-3及水等对该反应活性都有明显的抑制作用,提高反应温度有利于改善催化剂的反应性能.     

Evaluation of titanium dioxide as a pharmaceutical excipient for preformulation of a photo-labile drug: effect of physicochemical properties on the photostability of solid-state nisoldipine

To characterize the photocatalytic activity of TiO2 via solid-state reaction, the relationship between the physicochemical properties and photocatalytic activity of TiO2 was investigated and estimated from the results of photodegradation of nisoldipine. The photodegradation of nisoldipine was significantly enhanced by addition of TiO2. Two degradation products, nitroso-phenylpyridine derivative and nitro-phenylpyridine derivative, were formed. The degree of photocatalytic activity of TiO2 was quite different between the various types of TiO2 investigated, even when the crystalline phase was the same. As a result of the investigations into the relationship between the photocatalytic activity and physicochemical properties of TiO2, it was found that for the rutile form the photocatalytic activity has good correlation with specific surface area of TiO2, but poor correlation with water loss on drying of TiO2. However, for the anatase form, the photocatalytic activity has good correlation with water loss on drying of TiO2, but poor correlation with specific surface area. Moreover, it was found that the crystallinity of TiO2 has a moderate correlation with the photocatalytic activity of both crystal forms of TiO2. These results suggest that a degree of photocatalytic activity of TiO2 depends on the various physicochemical properties of each type of TiO2 investigated.     

活性炭负载TiO2-Fe3O4磁性光催化剂的制备及性能

采用溶胶-凝胶法制备了易于固液分离的活性炭（AC）负载磁性光催化剂（TiO2-Fe3O4／AC）．样品通过SEM-EDX和X射线衍射法进行表征．通过在紫外光照射下降解亚甲基蓝评价其光催化降解能力．结果表明：负载22％Fe3O4的光催化剂（含20％TiO2和58％AC）的光催化活性最强（120min时亚甲基蓝的降解率达到87％,是纯TiO2的2．7倍）;磁性光催化剂可实现磁分离回收．     

利用二氧化钛簿膜光催化降解废水(英文)

主要研究了在ＴｉＯ２薄膜上光催化降解有机磷废水。结果表明,镀膜基片不同、光催化时间不同、ＴｉＯ２晶型不同均对降解速率有影响。感兴趣的是可以利用太阳紫外光降解有机磷废水。     

氧缺位型TiO2的制备、表征及其光催化析氧活性

采用69 ℃饱和水蒸气和H2混合气, 于927 ℃下处理金红石型TiO2, 得到不同氧缺位的光催化剂, 并用X射线衍射(XRD)、比表面(BET)、电子顺磁共振(EPR)、紫外-可见漫反射(DRS)、光电子能谱(XPS)对其进行了表征. 考察了热处理时间对氧缺位型TiO2光催化分解水析氧活性的影响. 结果表明, 适量的氧缺位能显著提高金红石型TiO2光催化分解水的析氧活性, 其最大析氧速率达222 μmol·L-1·h-1.     

离子液体-水混合溶剂中制备纳米晶TiO2的结构特性及其光催化活性

以钛酸四丁酯为原料, 离子液体1-乙基-3-甲基咪唑醋酸盐([EMIM]+AcO-)-水为混合溶剂, 通过低温水热法制备了锐钛矿相TiO2纳米晶. 用XRD、N2吸附-脱附、XPS及UV-Vis漫反射等技术对产物的晶相、比表面积、表面性质及光吸收性进行表征, 并以甲基橙水溶液为研究对象, 考察了产物的光催化活性及催化剂用量、溶液酸碱度对其的影响. 结果表明, 离子液体鄄水混合溶剂中反应24 h 所得到的TiO2具有较高光催化活性, 并明显优于Degussa P25, 这一结果可归因于其具有较高的锐钛矿含量和较大的比表面积.     

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.     

二氧化钛光催化氧化-离子色谱法测定液晶材料中的氟含量

建立了TiO2光催化氧化-离子色谱法测定液晶材料中氟含量的方法。利用TiO2光催化氧化技术作为预处理手段对含氟液晶化合物进行有机破坏,使碳氟键断裂,生成的F-用离子色谱法测定。结果表明,TiO2催化剂用量为0.1g/L时,可达到最佳的光催化降解效果,最佳降解时间为50min。F-峰面积与其含量在0.005～1mg/g范围内呈良好的线性关系,检出限为2.1μg/g。测得3种液晶材料的氟含量分别为7.6,18.1及28.4mg/g,不同浓度的加标回收率为86.0%～118.0%,相对标准偏差RSD(n=5)在3.2%～5.7%之间。本方法不仅适用于有机氟体系,同时也为需经有机破坏后进行测定的有机化合物体系提供了新方法。     

TiO_2制备方法对光催化分解十二烷基苯磺酸钠的影响

本文以TiCl4 为前体 ,采用沉淀法、气相沉积法和溶胶 凝胶法分别制备了TiO2 光催化剂 ,比较了它们在十二烷基苯磺酸钠 (SDBS)光解反应中的催化活性。结果表明 ,以日光灯作光源时 ,气相沉积法获得的催化剂效果最好 ;以 5 0 0W紫外线高压汞灯作光源时 ,沉淀法获得的催化剂活性最高 ,10 0ml初始化学需氧量 (COD)为381mg/L的SDBS溶液 ,在 0 .1g催化剂作用下 ,室温光照 8h ,COD去除率可达 98 8%。在沉淀法制备的催化剂上 ,SDBS溶液的催化光解为一级反应     

Li+掺杂纳米TiO2的制备及其光催化性能研究

采用溶胶-凝胶法和浸渍法制备了Li⁺掺杂纳米TiO₂光催化剂,并用XRD和TEM等技术进行了表征;用pH值漂移法测量了催化剂的零电位pH值(pHpzc).结果表明,500℃煅烧制得的催化剂均为锐钛矿相;Li⁺的掺杂抑制了TiO₂粒子的生长,提高了催化剂的分散性;催化剂的零电位pH值为6.6—8.1,其值取决于Li⁺的浓度和掺杂方式.分别以紫外光和太阳光为光源,孔雀石绿和甲基橙为降解物评价了催化剂的光催化活性;并用气相色谱测试了污染物降解产生的CO₂的含量.结果显示,对孔雀石绿的降解,浸渍法和溶胶-凝胶法掺Li⁺都能有效提高TiO₂的光催化活性,但浸渍法比溶胶-凝胶法效果更好,催化活性最高的为浸渍法制备的5%(摩尔分数)Li⁺掺杂TiO₂,其在紫外光和太阳光下的光催化活性分别比纯TiO₂提高了6—8倍和9—10倍;对甲基橙的降解,除溶胶-凝胶法制备的3%(摩尔分数)Li⁺掺杂TiO₂能稍提高光催化活性外,其它Li⁺的掺杂都不同程度降低了TiO₂的光催化活性;随污染物降解率的增加,最终降解产物CO₂的含量增加.实验结果表明,Li⁺掺杂改变了催化剂表面的电荷状态从而改变了催化剂的零电位pH值是造成催化剂降解不同污染物具有不同催化活性的主要原因.     

陶瓷泡沫空气过滤器涂覆中孔TiO2薄膜用于室内空气净化中高效光催化降解NO

由于人们80%的时间呆在室内,室内空气的质量直接影响人类健康,因此近年来室内空气质量越来越受到人们的关注.室内污染物包括CO氮氧化物(NOx)和挥发性有机化合物(VOCs),它们给人体健康带来众多负面影响.更为重要的是,考虑到节能,现代建筑的空气密闭性大都较高,但这种减少吸入新鲜空气的设计直接导致室内各种污染物的累积.有些家用电器,如燃气灶和热水器,在使用的时候会涉及到煤、油和天然气的燃烧,特别是通风较差的情况下会成为室内主要的污染源.常规的治理技术,包括吸附和过滤,其成本相对较高,也不适用于低浓度污染物的治理.尤其是更换不及时的过滤器在排风系统中可能会成为VOCs的一个来源.因此,很有必要开发一种新型的技术以降低室内污染物的浓度和保持一个清洁的室内空气环境,从而保障人们的身体健康.光催化是去除室内空气污染物的有效方法.例如, TiO2、钛酸铋和钛酸锶等具有强氧化能力和稳定的光催化活性,因而是高效的光催化剂.一般而言,通常报道的TiO2光催化剂是高度分散的、或悬浮于液体介质中的细小颗粒或粉末.然而,粉末状的TiO2光催化剂不适宜于室内空气净化,因为它变得可吸入而对人体健康造成不利的影响.因此,人们尝试将TiO2颗粒作为薄膜固定在不同的刚性载体上,如玻璃、不锈钢和铝合金板.对基体进行涂覆可显著影响光催化时反应物的表面吸附行为.一般而言,光催化薄膜通常涂覆在平面上,如蜂窝空气过滤器.三维(3D)多孔的陶瓷泡沫对气体通过具有非常好的流体性质,因此本文以它作为涂覆的基体.这种陶瓷泡沫具有3D多孔结构,多种孔密度、比表面积和化学性质.3D多孔陶瓷泡沫空气过滤器的床层空隙率较高,因此使用时压降较低,且不像蜂窝空气过滤器,它具有复杂多变的孔结构,可增强流体的扰动和混合.另外,3D多孔陶瓷泡沫空气过滤器的开发多孔和网状的结构使得在催化体系具有非常好的气体动力学性质,催化剂表面和气体反应物有充分的接触.多孔材料在液相或气相催化反应中具有独特的优势,因此,陶瓷泡沫、多孔的氧化铝、多孔硅胶.分子筛和活性炭经常被用作催化剂载体.在固体基体上TiO2膜的形成可能使得TiO2光催化剂的有效比表面积降低,从而导致其光催化活性下降.然而,由于具有中孔结构的TiO2薄膜的比表面积大,其用于催化反应的活性位也更多,因此使用时仍然具有较高的活性.前期研究表明,涂覆在平面玻璃、不锈钢和氧化铝基体上的中孔TiO2薄膜用于环境净化时表现出增强的光催化效率.另外,室内环境中NO和NO2的浓度一般分别为几百个ppb之内和100 ppb以下.可见, NO是主要的室内空气污染物,对人体健康危害较大.基于此,本文首次采用反胶束法将中孔锐钛矿TiO2薄膜均匀一地涂覆在3D多孔高比表面积的泡沫过滤器上,采用X射线衍射、扫描电镜、X射线光电子能谱、N2吸附-脱附、紫外-可见光光谱和原子力显微镜对所制样品进行了表征,并将样品用于紫外光下催化降解NO,以揭示所制的中孔TiO2涂层具有高的比表面积和高的光催化活性,从而克服使用TiO2粉末所带来的不足.结果表明,由于中孔TiO2薄膜涂层具有较大的有效比表面积,其表面存在很多吸附活性位,用于吸附在反应过程中形成的水蒸汽、气相反应物和产物,因而具有更高的光催化活性,因此在陶瓷泡沫空气净化系统中可以高效地光催化NO降解：在所考察的不同孔密度的陶瓷泡沫过滤器涂覆的TiO2上400 ppb的NO单程转化率均在92.5%以上,高于涂覆在平面陶瓷砖上的TiO2.该陶瓷过滤器的3D多孔特性可增强流体的扰动和混合,使得气相反应物与光催化剂表面有着充分的接触;其大的孔密度也导致高的光催化速率.另外,本文所制样品在所有反应过程中均保持较高且稳定的NO降解速率,这表明其在NO降解反应中没有失活.     

水中硝基酚的纳米TiO_2光催化降解

以主波长254nm的紫外灯作为光源，研究了锐钛型纳米TiO2对邻硝基苯酚、2，4－二硝基苯酚的光催化降解行为，并与普通TiO2作了对比；结果表明，纳米TiO2表现出很高的光催化活性，催化降解过程符合一级动力学规律。     

SO2-4/TiO2固体酸催化剂的酸强度及光催化性能

SO2-4/TiO2固体酸可用于光催化降解溴代甲烷,其光催化性能明显优于TiO2光催化剂.在相同反应条件下,SO2-4/TiO2的光催化活性比TiO2提高2～10倍.当H2SO4浸渍液浓度为1mol/L时,制得的SO2-4/TiO2酸性最强(H0＜-12.14),具有超强酸性和最高的光催化活性.     

氢还原二氧化钛光催化降解磺基水杨酸的研究

研究了由偏钛酸在不同温度下焙烧制成的TiO2,经氢还原后用于光催化降解磺基水杨酸（SSal) 以及TiO2的漫反射光谱和荧光光谱特征。结果表明,锐钛型TiO2在经550℃ 氢还原处理120min后,光催化活性明显提高;600℃条件下焙烧制得的TiO2,经氢还原后其光催化降解SS al的反应活性最高。漫反射光谱结果表明,800℃条件下焙烧制得的TiO2,开始出现转晶现象,从锐钛型逐渐向金红石型过渡。TiO2荧光光谱的峰面积（F）和倍频峰面积（R）的比值越大。TiO2光催化降解SSal的活性越高,提出了氢还原后TiO2的光催化作用机制。     

Mesoporous Fe2O3-doped TiO2 nanostructured fibers with higher photocatalytic activity

Mesoporous Fe(2)O(3)-doped TiO(2) nanostructured fibers were fabricated through electrospinning the relevant gel precursor. The prepared fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and surface analysis, respectively. The photocatalytic activity of these mesoporous composite fibers was evaluated by photocatalytic degradation of methylene blue (MB) in water under UV irradiation. Compared with different types of photocatalysts, the 1% Fe(2)O(3)-doped TiO(2) fibers exhibited super photocatalytic activity.     

TiO2- and BaTiO3-assisted photocatalytic degradation of selected chloroorganic compounds in aqueous medium: correlation of reactivity/orientation effects of substituent groups of the pollutant molecule on the degradation rate

Investigation of the photocatalytic activity of BaTiO(3), a perovskite wideband gap semiconductor has been done in comparison with a widely used photocatalyst TiO(2) for the degradation of 4-chlorophenol (4-CP), 4-chloroaniline (4-CA), 3,4-dichloronitrobenzene (3,4-DCNB), and 2,4,5-trichlorophenol (2,4,5-TCP). BaTiO(3)/TiO(2) nanoparticles were prepared by gel-to-crystalline conversion method. BaTiO(3) has exhibited better catalytic efficiency and process efficiency compared with TiO(2) in most of the cases. The present research focuses mainly on two aspects: first the photocatalytic activity of BaTiO(3), as there are very few reports in the literature, and second the reactivity/orientation effects of substituent groups of the pollutant molecules on the degradation rate. The above chloroorganic compounds have at least one chlorine substituent in common, along with other functional groups such as -OH, -NH(2), and -NO(2). Furthermore, the effect of electron acceptors and pH on the rate of degradation is presented. The reactions follow first-order kinetics. The degradation reaction was followed by UV-vis, IR, and GC-MS spectroscopic techniques. On the basis of the identification of the intermediates, a probable degradation reaction mechanism has been proposed for each compound.     

碳掺杂的二氧化钛纳米管的制备及其可见光催化性能

以尿素作为碳元素前驱体对TiO2纳米管进行掺杂,采用比表面积测定、X射线衍射、透射电子显微镜、能量色散X射线荧光光谱、X射线光电子能谱、固体漫反射紫外-可见吸收光谱和荧光光谱对产物进行了表征。 结果表明,以尿素作为前驱体可制备C掺杂的TiO2纳米管,C掺杂后,TiO2纳米管的可见光催化活性明显提高。 此外,研究了C掺杂量、煅烧温度、催化剂用量和pH值对TiO2纳米管光催化降解活性的影响,发现当C的掺杂量为5.3%、催化剂用量为1.5 g/L、溶液的pH值为5时,在其催化作用下,可见光光照3 h后罗丹明B的降解率可达到91%。     

Synthesis, property characterization and photocatalytic activity of the novel composite polymer polyaniline/Bi2SnTiO7

A novel polyaniline/Bi(2)SnTiO(7 )composite polymer was synthesized by chemical oxidation in-situ polymerization method and sol-gel method for the first time. The structural properties of novel polyaniline/Bi(2)SnTiO(7) have been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray spectrometry. The lattice parameter of Bi(2)SnTiO(7) was found to be a = 10.52582(8) ?. The photocatalytic degradation of methylene blue was realized under visible light irradiation with the novel polyaniline/Bi(2)SnTiO(7) as catalyst. The results showed that novel polyaniline/Bi(2)SnTiO(7 )possessed higher catalytic activity compared with Bi(2)InTaO(7) or pure TiO(2) or N-doped TiO(2) for photocatalytic degradation of methylene blue under visible light irradiation. The photocatalytic degradation of methylene blue with the novel polyaniline/Bi(2)SnTiO(7) or N-doped TiO(2) as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01504 or 0.00333 min(-1). After visible light irradiation for 220 minutes with novel polyaniline/Bi(2)SnTiO(7 )as catalyst, complete removal and mineralization of methylene blue was observed. The reduction of the total organic carbon, the formation of inorganic products, SO(4)2- and NO(3-), and the evolution of CO(2) revealed the continuous mineralization of methylene blue during the photocatalytic process. The possible photocatalytic degradation pathway of methylene blue was obtained under visible light irradiation.     

Fixed-bed column studies of pentachlorophenol removal by use of alginate-encapsulated pillared clay microbeads

The high rate of electron/hole pair recombination reduces the quantum yield of the processes with TiO(2) and represents its major drawback. Adding a co-adsorbent increases the photocatalytic efficiency of TiO(2). In order to hybridize the photocatalytic activity of TiO(2) with the adsorptivity of carbon nanotube, a composite of multi-walled carbon nanotubes and titanium dioxide (MWCNT/TiO(2)) has been synthesized. The composite was characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared absorption spectroscopy (FTIR), and diffuse reflectance UV-vis spectroscopy. The catalytic activity of this composite material was investigated by application of the composite for the degradation of methyl orange. It was observed that the composite exhibits enhanced photocatalytic activity compared with TiO(2). The enhancement in photocatalytic performance of the MWCNT/TiO(2) composite is explained in terms of recombination of photogenerated electron-hole pairs. In addition, MWCNT acts as a dispersing agent preventing TiO(2) from agglomerating activity during the catalytic process, providing a high catalytically active surface area. This work adds to the global discussion of how CNTs can enhance the efficiency of catalysts.