空气中苯系物的TiO2光催化降解研究进展

本文对近年来空气中挥发性苯系物的TiO2光催化降解机理、TiO2光催化降解苯系物的主要影响因素以及TiO2的失活与再生方法等的研究进展进行了较详尽的评述,并对今后的研究工作进行了展望。     

Photocatalytic decomposition of tetrachloroethylene in the gas phase with titanium dioxide as catalyst

The gas phase photocatalytic destruction of tetrachloroethylene (PCE) was investigated by using an in situ photocatalytic reactor with FT-IR analysis in batch mode. The main products of PCE degradation are CO₂ and COCl₂, with trichloroacetylchloride as an intermediate. It was found that the rate of PCE degradation and the appearance of products in the gas phase are highly dependent on their adsorption properties on the surface of the catalyst, besides other reaction conditions, such as the intensity of irradiation and the composition of the reaction mixture.     

Dependence of the rate of photocatalytic decomposition of safranine on the catalyst concentration

The effect of the concentration of disperse titanium-containing oxide photocatalysts on the decomposition of safranine in aqueous solution was studied. The observed decomposition rate constant of safranine increases with increasing catalyst content in the solution and reaches a maximum at catalyst concentration ≤3 g/L, after which this constant no longer depends on the catalyst content. The plateau for the rate constant results from light scattering and narrowing of the reaction space due to increased optical density of the solution. An increase in the specific catalyst surface is observed in the region of a rising rate constant with increasing catalyst concentration, while no such dependence is found in the plateau region. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 104-107, March-April, 2009.     

掺氮二氧化钛可见光照射降解微囊藻毒素-LR

采用溶胶凝胶法制备了N掺杂TiO2(N-TiO2)纳米粉体光催化剂,利用X射线光电子能谱(XPS)、X射线衍射(XRD)、紫外可见反射光谱及透射电镜(TEM)分析测定,对光催化剂N/TiO2进行了结构表征.发现N掺杂TiO2相对纯TiO2禁带宽度变窄,可见光区有明显吸收.在可见光照射下,利用纳米N/TiO2作为光催化剂降解微囊藻毒素(Microcystin-LR,MC-LR),通过高效液相色谱仪(HPLC)跟踪检测降解过程MC-LR浓度变化,液质联用仪(LC-MS)检测MC-LR降解中间产物变化.利用电子自旋共振法(ESR)及过氧化物酶催化氧化方法跟踪定性定量测定光催化过程中氧化物种的种类变化.采用总有机碳(TOC)测定仪测定了MC-LR光催化深度氧化矿化效果.结果表明,可见光(λ420nm)照射可有效激发光催化剂N-TiO2活化分子氧降解MC-LR,在反应条件下,光催化反应14h,MC-LR降解率达到100%,20h矿化率达到59%.其光催化反应体系中氧化物种主要为羟基自由基(·OH).质谱检测到13种降解产物,主要反应机理为光催化反应产生·OH进攻MC-LR结构四个易氧化部位,以及一些氨基酸之间的肽键的水解.     

Influence of humidity and acidity of the titanium dioxide surface on the kinetics of photocatalytic oxidation of volatile organic compounds

The influence of the humidity and acidity of the TiO₂ surface on the kinetics of the photocatalytic processes of deep oxidation of volatile organic compounds was studied. At 20 °C the rates of acetone and benzene oxidation are maximum at the coverages of TiO₂ with water close to monolayer and are 3—5 times higher than that in the dry atmosphere. The activation energy of benzene oxidation (E _a = 6.3±0.4 and 43.0±3.2 kJ mol^–1 at relative humidities of 8 and 70%, respectively) at a humidity higher than 30% decreases according to the exponential law with an increase in the surface acidity when multilayer water films are formed on the surface. Under the real conditions of operation of photocatalytic air purifiers, a TiO₂ particle is covered by water nanofilms. As in aqueous solutions, photoprocesses on the TiO₂ surface depend substantially on the solvation of the participants of the reaction, the formation of the double electric layer, and the concentration of the electrolyte (due to the dissociation of the surface acid-base groups).     

Regularities of decomposition of organic vapors using a photocatalytic air cleaner

The kinetics of oxidation of vapors of model air contaminators, viz., acetone, ethanol, and heptane, was studied using a photocatalytic air cleaner. The composition of the oxidation products was determined, and the rates of oxidation of the starting substances were measured. The deep oxidation of the starting substrates to CO₂ and H₂O occurs until their concentration achieves a limiting value. At higher concentrations a “breakthrough” of the starting substrate is observed. Ethanol is oxidized with the formation of intermediate products. The experimental data obtained were approximated by a kinetic model, which includes stages of formation of intermediates and their competitive adsorption. The results of the approximation agree well with the experimental data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1812–1818, August, 2005.     

纳米二氧化钛光催化降解喹啉动力学

利用溶胶-凝胶法制备纳米二氧化钛光催化剂,探讨了其光催化降解废水中典型含氮杂环化合物喹啉的动力学行为。实验条件下,TiO₂光催化降解喹啉的反应为准一级反应,可用Langmuir-Hinshelwood动力学模型描述,其表达式为r=0.296kc_t/(1+0.296c_t),其中,lnk =-0.411 1lnc₀+2.278。     

Mechanism of photocatalytic oxidation of gaseous ethanol

A photocatalytic film reactor with a titanium dioxide film was used for oxidation of gaseous ethanol at 253.7 nm. The influences of partial pressures of oxygen and water vapour in different carrier gases were studied. The rate of photocatalytic oxidation of ethanol was significantly affected by the content of oxygen but water vapour had no effect. It was suggested that the photocatalytic transformation of ethanol follows a direct oxidation mechanism where the interaction of ethanol with positive hole gives first cationic free radical of ethanol, which is converted by multipathway reactions with oxygen to acetaldehyde, ethyl formate, and ethyl acetate.     

Mg-Al 类水滑石/二氧化钛异质复合纳米晶光催化氧化苯的性能

 采用过饱和沉淀法合成 n(Mg)/n(Al) = 2 的 Mg-Al 类水滑石化合物 (Mg-Al-HT), 再用水热法将它与钛胶复合, 制得 Mg-Al-HT/TiO2 异质复合光催化剂. 采用 X 射线粉末衍射、透射电子显微镜、场发射扫描电子显微镜、低温 N2 吸附-脱附、紫外-可见漫反射光谱和热重等技术对催化剂结构、成分和性质进行了表征. 结果表明, 在波长 365 nm 的紫外光照射降解苯的反应中, Mg-Al-HT/TiO2 异质复合光催化剂表现出优于单一的 TiO2 或 Mg-Al-HT 催化剂的光催化活性, 且稳定性更高; 同时讨论了该复合催化剂性能优异的原因. 另外, 运用电子顺磁共振技术检测到体系中存在羟基自由基等活性物种, 并据此提出了 Mg-Al-HT/TiO2 异质复合纳米晶催化剂光催化降解苯的反应机理.     

活性炭负载纳米TiO_2光催化降解甲醛废水研究

甲醛对人和温血动物的毒性很强,如果人类长期饮用被甲醛污染的水源,会引发头昏、贫血以及各种神经系统疾病.为此,研究学者对甲醛废水的处理进行了很多的试验研究.目前处理甲醛废水的主要方法有:芬顿法、光催化氧化法、湿式氧化处理等高级氧化技术,二氧化氯法,蒸汽吹脱法,氧化吸附法,SBR工艺等.     

甲酰胺对介孔N-TiO2微结构及光催化性能的影响

以钛酸四丁酯为前躯体,甲酰胺为氮源,采用溶胶凝胶法制备了具有可见光活性氮掺杂二氧化钛(N-TiO2)光催化剂.通过XPS、XRD、低温N2吸附.脱附和UV-Vis等表征,考察甲酰胺加入量对样品微结构和可见光活性的影响.当甲酰胺与钛酸四丁酯的物质的量的比为2、4、8、13时,制备的样品晶粒粒径在8～12 nm范围内,孔径在9～16咖范围内,孔隙率在54%～63%之间.甲酰胺与钛酸四丁酯的物质的量的比为13时,所制备样品具有较强的可见光吸收性能,其最大吸收边扩展到570 nm左右,禁带宽度减小至2.18 eV,比纯二氧化钛禁带宽度3.20 eV降低了1.02 eV.结果表明:随着甲酰胺加入量的增加,样品的晶粒粒径、孔径、孔隙率明显变大,禁带宽度减小.对甲基橙的室内自然光降解实验证明.氮掺杂二氧化钛具有良好的光催化活性,当甲酰胺与钛酸四丁酯的物质的量的比为13时,催化剂对甲基橙的降解率最高,为98.3%.     

金属组分对TiO2光催化氧化NO-2反应的影响

亚硝酸根离子;金属组分对TiO2光催化氧化NO-2反应的影响     

Synthesis of immobilized TiO2 nanowires by anodic oxidation and their gas phase photocatalytic properties

In this paper, anodic oxidation method was successfully employed to the direct growth of immobilized TiO₂ nanowires on titanium foil in ethylene glycol electrolyte solution contained HF and water. The morphologies of the TiO₂ nanowires could be tuned by changing the content of HF and water. The structures, morphologies and optical properties of TiO₂ nanowires were characterized by SEM, XRD, UV–vis and PL. It was found that the nanowires originally grew from the splitting of TiO₂ nanotubes. The gas phase photocatalytic activities were investigated by photodegradation of gaseous toluene under UV irradiation, and irregular TiO₂ nanowires showed the best photocatalytic ability.     

Preparation, characterization and photocatalytic activity of visible light driven chlorine-doped TiO2

A novel chlorine-doped titanium dioxide catalyst with visible light response was prepared by hydrolysis of tetrabutyl titanate in hydrochloric acid. The catalyst samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). Results showed that the doped element of Cl lowered the temperatures of phase transformation of TiO₂ from amorphous to anatase and from anatase to rutile. The absorption edge of chlorine-doped TiO₂ calcined at 300°C shifted to visible light region. X-ray photoelectron spectroscopy results proved that chlorine existed in the TiO₂ crystal lattice as anion. The photocatalytic degradation of phenol showed that under visible light (λ > 400 nm) irradiation, the chlorine-doped TiO₂ calcined at 300°C displayed the best performance, the degradation ratio of phenol was 42.5% after 120 min. Translated from Chinese Journal of Catalysis, 2006, 27(10): 890–894 [译自: 催化学报]     

碳和钇共掺杂对混相TiO2光催化性能的影响

TiO2因其毒性低、稳定性高、制备成本低廉而获得广泛应用,特别是作为光催化剂在降解环境污染物方面受到了广泛关注;然而,纯TiO2较大的光生载流子复合率和较宽的带隙限制了其应用.元素掺杂作为一种拓宽光催化剂光吸收能力的方法广泛应用于各种光催化剂的修饰改性,而两种具有光催化性能的TiO2相共存则能有效抑制光生载流子的复合,因此采取合适的方法有效利用这两种TiO2改性的方法制备得到更具实际应用潜质的光催化剂具有一定的可行性.本文通过简单的溶胶-凝胶过程向锐钛矿相与金红石相组成的混相TiO2中共掺杂碳和钇得到了一种活性较高的可见光响应光催化剂.采用粉末X射线衍射、拉曼光谱、X射线光电子能谱和透射电镜等表征手段研究了碳和钇掺杂对TiO2结构的影响,发现碳掺杂有利于金红石相的形成且材料具有更大的晶粒尺寸,钇掺杂则有利于锐钛矿相的形成且能细化材料的晶粒尺寸,提高材料的比表面积,导致材料更好的光催化活性.材料在30 W荧光灯光照条件下的光催化降解亚甲基蓝(MB)性能的研究显示,C-Y-TiO2样品具有比单掺杂和未掺杂样品更高的光催化活性,其顺序为C-Y-TiO2>Y-TiO2>C-TiO2>TiO2≈P25.此外,降解反应动力学研究表明C-Y-TiO2样品光降解MB的速率是未掺杂样品在相同条件下降解速率的3.5倍.不同钇掺杂含量样品的结构和光催化降解MB的研究结果表明,钇掺杂显著促进了锐钛矿相TiO2的形成.这说明钇可能仅掺杂进入锐钛矿相,因此合适的钇掺杂量才能有效形成最优化的光催化性能的混相TiO2.不同热处理温度下获得的样品的光降解MB特性也表明,一定的热处理温度有利于合适的锐钛矿相和金红石相的组成,从而有利于相间的协同效应.紫外-可见光谱和荧光光谱表征分析表明,碳和钇的掺杂都拓展了其吸收光谱到可见光区域,且抑制了光生电子和空穴对的复合,进而提高了材料的光催化活性.碳和钇共掺杂的混相TiO2具有较高可见光光催化活性的主要原因有两个方面:一是元素掺杂减小了TiO2的带隙使得材料具有可见光响应;二是金属和非金属元素在锐钛矿相与金红石相TiO2中不同的掺杂特性形成的协同效应,抑制了光生电子和空穴的复合.     

One-step fabrication and high photocatalytic activity of porous TiO2 hollow aggregates by using a low-temperature hydrothermal method without templates

Porous TiO2 hollow aggregates have been synthesized on a large scale by means of a simple hydrothermal method without using any templates. The as-prepared products were characterized by means of field emission scanning electron microscopy, XRD, TEM, nitrogen adsorption, UV/Vis diffuse reflectance spectroscopy, and FTIR spectroscopy. The photocatalytic activity of the aggregates was demonstrated through the photocatalytic degradation of Rhodamine B. Structural characterization indicates that the porous TiO2 aggregates are 500-800 nm in diameter and display mesoporous structure. The average pore sizes and BET surface areas of the aggregates are 12 nm and 168 m2 g-1, respectively. Optical adsorption investigations show that the aggregates possess an optical band-gap energy of 3.36 eV. The as-prepared products were substantially more effective photocatalysts than the commercially available photocatalyst P25. The dye degradation rate of the porous TiO2 hollow aggregates is more than twice that of P25. The high photoactivities of the aggregates can be attributed to the combined effects of several factors, namely, large surface areas, the existence of mesopores, and the high band-gap energy. In addition, the as-prepared products can be easily recycled.