二氧化钛薄膜上三氯乙烯光催化氧化反应机理

 研究了二氧化钛薄膜上三氯乙烯(TCE)气相光催化氧化的反应机理. 结果表明,TCE气相光催化氧化反应生成的氯气可引发TCE的连锁反应. 当添加氯气的浓度相同时TCE表面光催化反应的初速率约为光化学反应初速率的2倍,说明连锁反应主要发生在催化剂表面. 氯可吸附在催化剂表面,作为电子的接受体抑制空穴与电子复合,提高TiO2光催化剂的活性. 除了TCE与吸附在催化剂表面的·OH的相互作用及反应产物/中间产物二氯乙酰氯的光催化分解可生成氯气以外,光气在与氯气共存时的光分解也有利于氯的生成.     

三氯乙烯预处理的TiO2薄膜上挥发性有机物的光催化反应

 制备了TiO2薄膜催化剂,并用三氯乙烯对其进行了预处理; 采用FT-IR,GC/MS及XPS等技术研究了三氯乙烯预处理的TiO2薄膜上挥发性有机物的光催化反应. 结果表明,三氯乙烯预处理能加快某些挥发性有机物的光催化反应. 这是由于氯作为三氯乙烯气相光催化分解反应的中间产物吸附在催化剂表面,成为反应的活性物种引发挥发性有机物发生游离基反应,从而提高其气相光催化反应速率.     

紫外线预照射对TiO2上三氯乙烯气相光催化氧化反应的影响

 用紫外线照射法对TiO2光催化剂进行了预处理,并利用热重分析比较了预照射法和高温加热法对TiO2上三氯乙烯气相光催化氧化反应的影响. 结果表明,紫外线预照射可加快三氯乙烯的气相光催化反应. 这可能是紫外线预照射使TiO2 的表面状态和表面结构发生了变化,使催化剂表面活性基团羟基自由基的量增加所致.     

MnO_2对TiO_2光催化降解苯胺的影响

采用动力学方法研究了MnO2颗粒物对TiO2光催化降解苯胺活性的影响,对比考察了光催化降解过程中苯胺溶液的UV吸收光谱的变化,并用HPLC方法鉴别了中间产物.结果表明,少量MnO2颗粒物就能使TiO2光催化降解苯胺的活性受到明显的抑制,不同结构的二氧化锰致毒效应由大到小的顺序为:δ-MnO2α-MnO2β-MnO2;降解不同时间后溶液的UV吸收光谱的变化也反映了MnO2颗粒物具有同样的致毒效应;MnO2颗粒物不改变TiO2光催化降解苯胺的途径,但对生成中间产物的基元步骤的抑制程度不同。     

TiO_2/UV/O_2和TiO_2/UV/N_2体系降解水中对氯硝基苯

以商用TiO2P25为催化剂,分别在TiO2/UV/O2和TiO2/UV/N2两种体系下进行降解对氯硝基苯(pCNB)试验.采用ESR对两种体系下光催化反应形成的.OH进行测定,利用LC-MS对两种体系下反应形成的中间产物进行了定性和定量分析,最后对pCNB降解过程中氯和硝基的存在形式进行了研究.结果表明:TiO2/UV/O2体系的催化降解效果要明显优于TiO2/UV/N2体系;两种反应体系都有.OH产生,并且TiO2/UV/O2体系产生的.OH的量多于TiO2/UV/N2体系产生的.OH的量;TiO2/UV/O2体系形成的中间产物的种类要多于TiO2/UV/N2体系形成的,苯环上的氢、氯、硝基均可被.OH取代形成对硝基酚(pNP)、5-氯-2-硝基酚(5-C-2-PN)等酚类物质;两种体系下均有Cl-和NO2-存在,其中Cl-生成势与pCNB的去除势一致,只有TiO2/UV/O2体系中存在NO3-.     

TiO2/BixTiyOz气相光催化降解苯的动力学模型及反应机理

在密闭不锈钢反应器内考察了TiO2/BixTjyOz催化剂气相光催化降解苯的性能.结果表明,TiO2负载于Bi12TiO20,Bi2Ti2O7和Bi4Ti3O12上制成的催化剂,光催化活性得到很人的提高,TiO2最佳负载量为2.0%;其中,TiO2/Bi12TiO20的光催化活性最高,苯最高转化率是纯TiO2的2倍,催化剂使用寿命也延长了1倍.在本文实验条件下,TiO2/Bi12TiO20上苯气相光催化降解符合Lang-muir-Hinshelwood动力学模型,光催化反应速率常数k和Langmuir吸附常数K分别为0.006 4mg/(L·min)和9.670 2L/mg.采用红外光谱对失活的催化剂进行表征,结果表明催化剂表面出现了羰基与羟基等的振动峰,同时检测到主要的中间产物是2,6-二叔丁基-4-甲基苯酚,它吸附在催化剂表面活性化上而导致催化剂失活.最后推测了苯在催化剂表面气相光催化降解的反应机理.     

甲基叔丁基醚光催化降解的反应历程

以自制的TiO2为催化剂,在间歇式光催化反应装置中考察了水中甲基叔丁基醚的光催化降解反应.结果表明,水中MTBE在TiO2催化剂、氧气和紫外光照射的条件下能被光催化转化成无毒产物并最终被矿化.MTBE光催化降解过程中产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮,尽管降解速率不同,它们也都能被光催化降解.通过对反应物、中间物及产物的追踪分析,认为MTBE的光催化降解首先是通过羟基化过程来进行,进而提出MTBE光催化降解的可能反应历程.     

SnO_2/TiO_2纳米管复合光催化剂的性能及失活再生

基于微波水热法和微乳液法合成SnO2/TiO2纳米管复合光催化剂.通过X射线衍射(XRD)、配有能量色散X射线光谱仪(EDX)的透射电镜(TEM)和电化学手段对光催化剂进行表征.以甲苯为模型污染物,考察光催化剂在紫外光(UV)和真空远紫外光(VUV)下的性能及失活再生.结果表明,SnO2/TiO2纳米管复合光催化剂形成三元异质结(锐钛矿相TiO2(A-TiO2)/金红石相TiO2(R-TiO2)、A-TiO2/SnO2和R-TiO2/SnO2异质结),促使光生电子-空穴对的有效分离,提高光催化活性.SnO2/TiO2表现出最佳的光催化性能,UV和VUV条件下的甲苯降解率均达100%,CO2生成速率(k2)均为P25的3倍左右.但由于UV光照矿化能力不足,中间产物易在催化剂表面累积.随着UV光照时间的增加,SnO2/TiO2逐渐失活,20 h后k2由138.5 mg·m-3·h-1下降到76.1 mg·m-3·h-1.利用VUV再生失活的SnO2/TiO2,过程中产生的·OH、O2-·、O(1D)、O(3P)、O3等活性物质可氧化吸附于催化剂活性位的难降解中间产物,使催化剂得以再生,12 h后k2恢复到143.6 mg·m-3·h-1.UV和VUV的协同效应使UV降解耦合VUV再生成为一种可持续的光催化降解污染物模式.     

TiO2/AC复合光催化剂对苯和丁醛的气相光催化降解机理

 利用溶胶-凝胶并水热处理法制备了TiO2光催化剂和TiO2/AC复合光催化剂,在静态光催化反应器中研究了苯和丁醛的气相吸附和光催化降解,利气相色谱分析确定了生成的中间体. 结果表明, TiO2/AC复合光催化剂比TiO2光催化剂具有较强的吸附能力和较高的光催化活性; 在TiO2和TiO2/AC上,苯(或丁醛)光催化降解产生相同的中间体,表明在两种催化剂上发生的光催化反应遵循相同的机理,进而讨论了其可能的光催化氧化途径.     

ZnO和TiO2粒子的光催化活性及其失活与再生

 利用XRD，TEM，BET和UV－Vis等测试技术对商品的ZnO及TiO2和纳米ZnO及TiO2粒子进行了表征．无论是商品的还是纳米的，在光催化氧化降解气相n－C7H16和SO2及液相苯酚的反应中，TiO2均表现出比ZnO高的光催化活性，并从光腐蚀性和表面电荷两方面分析了其原因．在光催化氧化降解n－C7H16的反应中，ZnO粒子易失活，而TiO2粒子不易失活．但是，在光催化氧化降解SO2的反应中，ZnO和TiO2粒子均易失活．SPS和XPS测试结果表明，光催化剂表面的导电类型由反应前的n型变成了失活后的p型．这主要是由于反应产物发生吸附所致．失活后的光催化剂可以通过浸洗和干燥再生．     

Distance dependence of the photocatalytic efficiency of TiO2 revealed by in situ ellipsometry

Spectroscopic ellipsometry was utilized to follow in situ photodegradation of organic species in the vicinity of TiO(2) nanoparticles during UV irradiation. Stacked layers composed of TiO(2), mesoporous SiO(2), and mixed mesoporous SiO(2)/TiO(2) nanocomposites with controlled thickness and porosity were used as model materials. Lauric acid molecules and poly(vinyl chloride) (PVC) layers were used as model mobile and immobile pollutants, respectively. The local photocatalytic activity was deduced by monitoring the variation of the thickness and refractive index of each independent layer. We show that the photocatalyzed degradation of an organic pollutant takes place only when the latter is located in close vicinity to the TiO(2) nanoparticle surface or can naturally diffuse toward it. As a result, the reaction efficiency is directly related to the organic pollutant diffusion. We also show that the distance of photocatalysis efficiency (d(s)) at which radical intermediates are still present and active is <10 nm from the TiO(2) surface under the conditions of the experiments. This was confirmed by the fact that an immobile condensed organic phase such as PVC was protected from the photocatalytic degradation when separated from the TiO(2) by a 20 nm layer of mesoporous silica.     

Mechanistic studies of the photocatalytic oxidation of trichloroethylene with visible-light-driven N-doped TiO2 photocatalysts

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (lambda > or = 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogen-doped TiO2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (lambda > or = 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product, only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.     

Kinetics of heterogeneous photocatalytic degradation of reactive dyes in an immobilized TiO2 photocatalytic reactor

The photocatalytic degradation of two reactive dyes has been investigated by UV/TiO2/H2O2 using an immobilized TiO2 photocatalytic reactor. Reactive Blue 8 (RB 8) and Reactive Blue 220 (RB 220) textile dyes were used as model compounds. Photocatalytic degradation processes were performed using a 5-L solution containing dyes. The initial concentrations of dyes were 50 mg/L. The radiation source was two 15 W UV-C lamps. A batch mode immersion photocatalytic reactor was utilized. UV-vis and ion chromatography (IC) analyses were employed to obtain the details of the photodegradation of the selected dyes. Colored synthetic waters were completely decolorized in relatively short time after UV irradiation in the presence of various concentrations of hydrogen peroxide. Formate, acetate, oxalate, and glyoxylate anions were detected as dominant aliphatic intermediates where they were further oxidized slowly to CO2. The UV/TiO2/H2O2 process was able to oxidize the dyes with partial mineralization of carbon, nitrogen, and sulfur heteroatoms into CO2, NO3-, and SO4(2-), respectively. Kinetics analysis indicates that the photocatalytic decolorization rates of the dye can be approximated by a pseudo-first-order model. The UV/TiO2/H2O2 process proved to be capable of decolorization and mineralization of the reactive dyes (RB 8 and RB 220).     

掺铈纳米TiO2薄膜制备及光催化降解甲醛甲苯

通过Sol-Gel工艺在玻璃表面及多孔陶瓷表面制得了均匀透明的掺铈纳米TiO2薄膜．通过SEM、XRD及UV-Vis等手段对玻璃表面掺铈纳米TiO2薄膜进行了表征．结果表明，薄膜表面无开裂现象、膜内部比表面积大、TiO2分布均匀．薄膜中出现的锐钛矿相在(101)面有一定的择优取向，且UV-Vis研究表明，掺铈纳米TiO2薄膜在近紫外的吸光度有明显提高．利用自行设计的反应器，以多孔陶瓷为介质，对甲醛、甲苯等有机物进行了光催化降解研究．结果表明，掺铈纳米TiO2薄膜对甲醛甲苯有极高的光催化降解效率，由于薄膜成本低廉，易于工业化，为净化室内空气开辟了新的途径．     

Novel one step hydrothermal synthesis of TiO2/WO3 nanocomposites with enhanced photocatalytic activity

A novel and simple one step hydrothermal process is used to prepare TiO(2)/WO(3) nanocomposites, in which WO(3) and TiO(2) are present in hexagonal and anatase crystalline forms, respectively, and have enhanced photocatalytic activity towards trichloroethylene degradation in the gas phase.     

TiO2薄膜光催化降解4-(2-吡啶偶氮)间苯二酚的研究

为了探索有机物４－（２－吡啶偶氮）间苯二酚（ＰＡＲ）,在固定光催化剂上的降解行为,采用溶胶一凝胶法,在玻璃表面制得均匀透明的纳米ＴｉＯ２薄膜,并以其作光催化剂,在２５４ｎｍ紫外光照射下,进行ＰＡＲ水溶液的光催化降解研究。研究了ＰＡＲ光催化降解率与溶液ｐＨ值、ＰＡＲ初始浓度、助催化剂（Ｈ２Ｏ２）浓度和不同光照条件的变化关系,得出了ＴｉＯ２薄膜的光催化降解ＰＡＲ的有利条件。     

影响TiO2薄膜光催化降解亚甲基蓝的因素

 用中频交流反应磁控溅射技术制备了具有良好光催化性能的TiO2薄膜,考察了紫外光源、反应器和溶液浓度对亚甲基蓝溶液光催化降解特性的影响. 结果表明,紫外光源对TiO2薄膜光催化降解性能有较大的影响; 在计算光催化降解速率时应充分考虑光解和光氧化的影响. 低压汞灯TUV为光催化降解的较好选择. 动态反应系统可以有效避免光解,显著提高光催化反应速度. TiO2薄膜具有很好的光催化性能,且性能稳定.     

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．