Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

光催化降解乐果的动力学研究

采用30 W石英紫外灯作为光源,研究了乐果在二氧化钛悬浮体系中光催化降解反应的动力学规律。考察了乐果起始浓度、TiO2用量、溶液pH值及温度对乐果光催化降解速率的影响,结果表明,乐果光催化降解符合表观零级动力学规律。由于速率常数k与乐果起始浓度有关,表明乐果光催化降解反应不是一个简单的零级反应。     

天然金红石光催化降解藏红T实验研究

以低压汞灯为光源研究了天然金红石悬浆体系中藏红T的脱色条件及其光催化反应动力学，讨论了溶液初始pH值、催化剂投入量、光强、气流量、催化剂粒径、反应气氛等实验条件对藏红T脱色速率的影响，阐述了实验过程中无机离子的生成情况。结果表明，该反应基本上符合一级反应动力学；在酸性条件下尤其是当溶液初始pH值为2．5时，藏红T的脱色速率要比在碱性和中性条件下快得多；增加光强度能较大地提高反应的降解速率；催化剂最佳投入量为1．3g／L；在氧化气氛下该反应比在非氧化气氛快得多；通入气体的流量在40L／h最合适；反应溶液中有氯离子溶出说明有机物中的含氯部分被降解。本研究为光催化作用降解有机污染物提供了新的途径。     

同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.     

纳米 Fe2O3-SnO2 光催化降解海水养殖废水中的氨氮

通过共沉淀法制备纳米Fe_2O_3-SnO_2光催化剂,采用XRD、SEM等测试手段对其进行形貌、物象、粒径一系列的表征,研究结果显示制得的催化剂仍保持纯SnO_2四方金红石型结构.研究了Fe_2O_3-SnO_2光催化剂投加量、Fe_2O_3与SnO_2物质的量比、煅烧温度、煅烧时间、氨氮初始浓度、p H值、H2O2浓度以及光照反应时间等因素对海水养殖废水中氨氮降解效率的影响.在紫外光照射下进行正交实验,确定最优化反应条件:催化剂投加量为0.4 g/dm3,煅烧时间为3 h,物质的量比为1∶2,氨氮初始含量为50 mg/dm3,光照反应时间为2 h.这5个因素对Fe_2O_3-SnO_2光催化氧化速率影响的大小程度依次为:Fe_2O_3与SnO_2物质的量比煅烧时间Fe_2O_3-SnO_2光催化剂投加量氨氮初始浓度光照时间.氨氮去除率可以达到85.1%,相同条件可见光下也可达到82.3%.     

泡沫镍基P-25薄膜光催化降解水中喹啉

为了提高TiO²薄膜的光催化效率和使用稳定性,采用浸渍涂布法将粉体P-25 TiO₂负载在泡沫镍基片上,制备泡沫镍基负载P-25薄膜光催化材料,利用XPS和FE-SEM分析了薄膜的晶相和形貌,并考察了不同条件下P-25薄膜对水中喹啉的降解效能。研究发现：P-25薄膜均匀覆盖泡沫镍基片表面,薄膜呈混晶结构,表面呈现微裂痕。实验表明：增大光照强度和曝气量能够明显提高水中喹啉的光催化降解率;低pH有利于水中喹啉的去除;初始浓度和温度不是光催化反应的主控因子;曝气产生的吹脱、扰动和水力紊流效应对光催化反应的影响不明显。结果显示：不改变水溶液温度和pH条件下,P-25薄膜对水中喹啉有良好的去除效果,并可多次重复使用。     

硅烷偶联剂改性TiO2/膨胀石墨复合材料的制备及其光催化性能研究

以硅烷偶联剂黏结剂,利用溶胶-凝胶法将TiO2（P25）负载在膨胀石墨上,利用XRD、EDS以及SEM等分析技术对TiO2/膨胀石墨复合材料进行表征;以橙黄Ⅱ为目标降解物,考察了TiO2/膨胀石墨复合材料光催化性能以及重复使用性能。结果表明：随着TiO2含量的增加,TiO2/膨胀石墨复合材料的光催化效率随之增加,对橙黄Ⅱ的光催化降解符合一级反应动力学方程,TiO2负载量为15%时,反应速率常数为0.387 h-1,高于P25的反应速率常数。TiO2/膨胀石墨复合物使用4次仍保持较高的光催化活性。     

Absorption and Photocatalytic Degradation of Machine Oil by Exfoliated Graphite-Supported Nanometer TiO2 Material

By loading nanometer anatase onto exfoliated graphite with the sol-gel method, exfoliated graphite-TiO2 composite （EG-TiO2） can be prepared, which can adsorb oil and can also degrade oil. In a technologic condition for preparing EG-TiO2, the impregnated number of times is the most important factor to influence oil-adsorbing capability, that is, when the impregnated number of times increases, the amount of saturation-adsorbed oil decreases. The study of EG-TiO2 photocatalytic degradation of machine oil based on the weight-loss method and infrared spectrum method indicates that EG-TiO2 has obvious effect of photocatalytic degradation for machine oil. Its performance is superior to pure nanometer TiO2 powder because nanometer TiO2 in EG-TiO2 has three-dimension laminar structure and comparatively high adsorption capability.     

Structural characteristics of zeolite/TiO2 composite and photocatalysis of toluene degradation

Zeolite/TiO2 composite photocatalysts were prepared by adding a certain amount of mordenite in TiO2, and degradation experiments on toluene through photocatalytic reactions were implemented. In this paper, these photocatalysts were characterized by using SEM, IR, RAMAN, XRD and UV-Vis to shed light on the microstructure and photocatalytic performance of the composite photocatalysts. The results indicated that the structural hydroxy of zeolite can participate in bonding reaction with TiO2, the addition of zeolite can greatly reduce the diameter of nanometer TiO2 particles in the composite photocatalysts, and enhance the ultraviolet light absorptance of the composite photocatalysts. When the percentage content of zeolite reached 20%, the photocatalytic performance of this catalyst would be highest, with the toluene conversion rate up to 94.58%.     

MnO2-UV联用光化学降解苯酚废水的初步研究

探讨了人工合成的高价锰氧化物与紫外光(UV)联用时降解苯酚废水的特性。结果表明,氧化锰矿物在无UV时对苯酚的降解能力差异大,1 g/L的氧化锰4 h对200 mg/L苯酚废水的降解率和COD去除率分别为:锰钾矿97.51%、酸性水钠锰矿89.07%、碱性水钠锰矿11.36%、钙锰矿9.67%;锰钾矿87.79%、酸性水钠锰矿53.11%、碱性水钠锰矿6.42%、钙锰矿1.43%。UV光照下,氧化锰矿物对苯酚的降解率有不同程度的提高,且表现出显著的表面光催化性质,增加了苯酚的深度降解,COD去除率显著提高。UV下氧化锰4 h对苯酚的降解率分别为:锰钾矿99.48%、酸性水钠锰矿91.86%、碱性水钠锰矿40.15%、钙锰矿35.95%);COD的去除率分别为:锰钾矿98.11%、酸性水钠锰矿68.45%、钙锰矿27.57%、碱性水钠锰矿24.27%。MnO2-UV联用时降解苯酚可能包括两种主要作用机制:氧化锰矿物的直接化学氧化降解和UV下MnO2的表面光催化降解。