网络状纳米氧化锌光催化降解水中有机染料的研究

在太阳光照射条件下用自制的网络状纳米氧化锌对不同有机染料溶液的降解性能作了系统的研究。结果表明,网络状纳米氧化锌对弱碱性有机染料溶液的降解效果较好。本文还比较了自制网络状纳米氧化锌与纳米二氧化钛对有机染料的降解性能,氧化锌的降解效果明显优于二氧化钛。     

水热法制备ZnO纳米棒及其光催化性能研究

以Zn(acac)2.H2O为单源前驱体,采用水热法在140℃条件下制备了ZnO纳米棒,并用XRD、SEM、TEM等测试手段对其进行了表征。利用紫外—可见分光光度计测试了其光吸收性能,发现ZnO纳米棒对200-400 nm波长范围的光有很强的吸收性,在可见光范围内,也有较强的吸收。以ZnO纳米棒为光催化剂对有机染料酸性红4B进行了光催化降解实验,并研究了光源、污水浓度对ZnO纳米棒光催化氧化效果的影响。研究结果表明,在日光照射180 min后,对酸性红4B的降解率接近100%。     

纳米TiO2 的制备及其光催化降解性能

采用低温水解沉淀法以TiCl4为原料制备了纳米TiO2,其结构经TEM和XRD表征。研究了太阳光激发下纳米TiO2对甲基橙的光催化降解性能,结果显示：纳米TiO2的分散性越好,粒径越小,光催化降解能力越强;以锐钛矿为主的复合纳米TiO2晶体比纯锐钛矿晶相具有更优异的光催化活性。     

模拟太阳光下稀土Gd掺杂了TiO2纳米晶的光催化性能研究

以甲基橙的光催化降解为探针反应,采用氙灯模拟自然条件下的太阳光,评价了通过酸催化的溶胶-凝胶法制备的稀土Gd掺杂改性TiO2纳米晶的光催化活性及对甲基橙水溶液TOC的去除效果.运用XRD和UV-Vis DRS表征技术考察了Gd掺杂对纳米TiO2的微晶尺寸、晶体结构与光学性能的影响.结果表明,Gd掺杂可以抑制TiO2由锐钛矿相向金红石相的转变,阻碍TiO2晶粒增长,使TiO2的光吸收带边发生蓝移且有利于对可见光的吸收,从而使Gd掺杂TiO2在模拟太阳光下光催化降解甲基橙的能力得到明显提高,但样品对甲基橙水溶液TOC的去除效果要滞后于其对色度的去除.     

纳米TiO2低温制备及光催化降解有毒有机污染物

通过设计不同的实验方案低温（180℃）制备得到纳米TiO2,并在紫外光（λ≤387nm）照射下利用有机染料罗丹明B（Rhodamine B,RhB）光催化降解为探针反应,以有机污染物降解活性最佳为目的,优选低温制备得到纳米TiO2最佳方案．结果表明以Ti（SO4）2为原料,在低温条件下通过蒸汽热法制得TiO2为最佳方案．对制备高催化活性的纳米TiO2利用透射电子显微镜（TEM）,X射线衍射仪（XRD）对其进行了物理特性及光化学性质的初步表征,探讨了纳米TiO2制备时反应温度和反应时间对其粒径大小、晶型转变以及光催化活性的影响．实验结果表明：在以紫外光（λ≤387nm）照射下的探针反应有良好的光催化降解效果为条件,优选低温制备得到纳米TiO2最佳反应温度为180℃,最佳反应时间为12h．通过紫外-可见光谱（UV—vis）、红外光谱（FTIR）和总有机碳（TOC）的测定分析,发现UV／TiO2体系在pH=3．00的条件下,能使RhB发生有效的降解和矿化,矿化率达到93．2％．     

钆及双稀土元素掺杂TiO2可见光催化降解罗丹明B的研究

以钛酸丁酯为前驱体，采用溶胶一凝胶法制备了钆及双稀土元素共掺杂纳米TiO2光催化剂，研究了自制催化剂在可见光下对有机染料罗丹明B催化降解反应的活性。稀土掺杂后的TiO2在可见光下催化活性比纯的TiO2有显著的提高。当Gd^3＋与TiO2的摩尔比为1．5％，催化剂经过500℃焙烧，对罗丹明B的降解率达到99．5％；Gd^3＋：La^3＋：TiO2的摩尔比为O．5：0．5：100，焙烧温度为600℃，降解率高达99．9％，比双元素掺杂的结果更好。     

ZnO/TiO2纳米管复合材料的制备及光电化学性能研究

采用电化学阳极氧化法制备TiO2纳米管,然后用光化学沉积法在TiO2纳米管表面沉积ZnO纳米颗粒制备ZnO/TiO2纳米复合材料。对样品进行了Raman谱、XRD和SEM表征,通过测定光电流-时间(I-t)和开路电压-时间(OCPT)曲线对ZnO/TiO2纳米复合材料的光电化学性能进行研究。结果表明,沉积ZnO没有改变TiO2的相结构;复合ZnO提高了TiO2的光电性能;在Zn(NO3)2浓度为10-3 mol.L-1的条件下制得的ZnO/TiO2纳米复合材料具有较好的光电性能。     

高性能光催化降解聚乙烯薄膜的研究

利用酸性蓝BGA染料敏化的纳米TiO2作为光催化剂, 与低密度聚乙烯(LDPE)树脂复合制备了具有可见光催化降解性能的复合塑料薄膜. 采用SEM、FTIR、VHX-100数码显微镜和高温凝胶渗透色谱(HTGPC)等分析技术系统地研究了该塑料薄膜在紫外光和太阳光照射下的降解性能. 探讨了塑料薄膜在光辐照前后的力学性能、质量和分子量变化规律. 研究结果表明, 该薄膜在经紫外线照射5 d后质量损失达到17.6％, 数均分子量由21800降低为5900; 经太阳光照射48 d后质量损失达到12.5％, 分子量降为8100. 辐照后薄膜拉伸强度和断裂伸长率显著降低, 羰基含量升高.     

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70min后乙醛被完全降解.     

阳离子表面活性剂体系中纳米TiO2的合成及表征

在阳离子表面活性剂双十八烷基二甲基氯化铵(D1821)的水溶液中,以钛酸四丁酯为钛源,在室温下合成了具有日光催化性能的纳米TiO2,考察了合成条件(反应温度、pH值、焙烧温度)对产物结构的影响。通过x射线衍射、透射电镜对所合成的样品进行表征,并对非离子表面活性剂壬基酚聚氧乙烯醚(NPE-10)进行了光催化降解性能研究。结果表明:反应温度为20℃,pH=7,焙烧温度为500℃时所合成的样品颗粒分散均匀,晶型完整,而且形成了锐钛矿和金红石的混晶结构。日光照射下,这种纳米TiO2对NPE-10表现出了较好的光催化性能,3h的降解率达到了80%。     

Minireview: Silver-Doped Titanium Dioxide and Silver-Doped Zinc Oxide Photocatalysts

The catalytic oxidation of organic dyes using various systems has been widely reported during the past decade. Photocatalytic methods, heterogeneous processes for the degradation of dyes, are one of the best and efficient oxidation processes to treat industrial wastewater with minimal residual waste. This review describes the improvement in catalytic activity of silver-doped titanium dioxide and silver-doped zinc oxide. The degradation of dyes provides information about the catalytic performance of silver-doped metal oxide. The effects of pH, catalyst concentration, dye concentration, hydrogen peroxide, dissolved oxygen, temperature, irradiation time, and light source have been reviewed along with the degradation mechanism and reaction methodology of organic dyes.     

Photocatalytic degradation of wastewater pollutants: titanium dioxide mediated degradation of methyl orange and beta-naphthol orange

The photocatalytic degradation of azo dyes such as methyl orange and beta-naphthol orange in aqueous suspensions of TiO2 has been investigated under a variety of conditions. The kinetics of degradation was studied under different conditions such as reaction pH, substrate and catalyst concentration, and types of titanium dioxide used and in the presence of electron acceptors and electron donors. The degradation rates of the dyes have been found to be strongly influenced by all the above parameters. Carbon dioxide yield measurements indicate that only partial mineralization occurs in the initial phase of oxidation.     

The effect of titanium dioxide exposure on the thermal properties of Zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) bones

This article presents the changes in the thermal properties of the control and titanium dioxide (TiO₂), both nano and bulk exposed Zebrafish bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The titanium dioxide exposed bones present a different thermal behaviour compared to the control bones. The residue masses are found to be increased due to titanium dioxide exposure. In particular, nano titanium dioxide exposure increases the residue mass level significantly (three fold) when compared to titanium dioxide bulk exposure. These thermal characteristics can be used as a qualitative method to check the metal oxide intoxication in biological samples.     

Heterogenous solar photocatalysis of two commercial reactive azo dyes

Two commercial reactive azo dyes--Reactive Black 5 (RB5) and Reactive Orange 16 (RO 16) have been treated by titanium dioxide and Zinc oxide photocatalysts separately under presence of sunlight. It is observed that solar photocatalytic treatment is effective in terms of colour and COD. The photodegradation efficiency of zinc oxide is comparable with TiO2 at pH 5-6 for RO16. The extent of decolourization and degradation of RB5 is greater in presence of zinc oxide photocatalyst than TiO2 at pH 5- 6. Zinc oxide undergoes <1% photodissolution after 6 hours of solar irradiation at working pH.     

用高温热水解法制备高活性TiO2纳米微晶光催化剂

采用钛酸四西酯在有机溶剂中高温热水解与结晶同时进行的方法，制备了二氧化钛纳米微晶光催化剂．以XRD、BET、TEM、TG和DTA等方法对获得的微晶进行了表征．所制得的TiO2纳米微晶平均值径约为12nm，比表面积在100m2·g-1以上，并能在报宽的煅烧温度范围内保持锐钛矿型晶体结构．将它应用于光分解甲基橙，具有高的光催化活性．     

Unusual photoreactivity of zinc oxide irradiated by concentrated sunlight

The decrease of fluorescence emission of phenol was studied in the presence of photoactive oxides (TiO₂, ZnO and Fe₂O₃) irradiated with a sodium lamp, direct sunlight (1 sun) and concentrated sunlight (40–50 suns) in aqueous solutions. As expected photodegradation of phenol was seen to be faster for all of the oxides irradiated by concentrated sunlight. The photodegradation capacity of titanium dioxide (TiO₂) is superior to that of zinc oxide (ZnO) and ferric oxide (Fe₂O₃) under a sodium lamp and direct sunlight, but ZnO is found to be as reactive as TiO₂ under concentrated sunlight. It has been shown that ZnO is a low cost alternative solar photocatalyst to TiO₂ for degradation of organics in aqueous solutions.     

Investigation of photocatalytic effect of SnO2 nanoparticles synthesized by hydrothermal method on the decolorization of two organic dyes

Tin oxide nanoparticles about 4 nm in size were successfully synthesized using hydrothermal method. The photocatalytic activity of the particles was determined by the decolorization of malachite green (MG) and titanium yellow (TY) under UV light. 12 ppm of MG and TY were used for the solution with an initial volume of 100 mL. The amounts of catalysts were 10, 30 and 50 mg. The effect of the catalyst loading on the reaction kinetic parameters and the decolorization rate constants (k) were determined. In order to reveal the photocatalytic efficiency of the nano particles, further experiments were conducted with bulk SnO(2). The oxygen species registered no observable effect on the reaction mechanism as nitrogen bubbling leads to no change in decolorization rates. Results showed that the synthesized nano tin oxide particles represent excellent photocatalytic activity for the decolorization of 12 ppm MG under UV light with 150 min of irradiation time. The energies of the highest occupied molecular orbital (HOMO) E(HOMO) of the dyes were also calculated by using the quantum chemical software in order to discuss the differences for the decolorization of two dyes. Electrical energy efficiency values for the decolorization of two dyes were also calculated.     

Photocatalytic degradation of azo dyes catalyzed by Ag doped TiO2 photocatalyst

In this paper, photocatalytic degradation of commercial textile azo dyes catalyzed by titanium dioxide and modified titanium dioxide with Ag metal (1% w/w) in aqueous solution under irradiation with a 400 W high-pressure mercury lamp is reported. The effect of various parameters such as irradiation time of UV light, amount of photocatalyst, flow rate of oxygen, pH and temperature for the Ag-TiO₂ photocatalyst were investigated. Kinetic investigations of photodegradation indicated that reactions obey improved Langmuir-Hinshelwood model and pseudo-first-order law. The rate constant studies of photocatalytic degradation reactions for Ag-TiO₂ and TiO₂ photocatalysts indicated that in all cases the rate constant of the reaction for Ag-TiO₂ was higher than that of TiO₂.     

Cationic dye-sensitized degradation of sodium hyaluronate through photoinduced electron transfer in the upper excited state

The formation of ground-state complexes of methylene blue (MB) and thionine (TN) with sodium hyaluronate (NaHA) was clearly observed by means of absorption spectra in aqueous solution. Irradiation of the complexes using 313 nm light caused significant degradation of NaHA under oxygen and argon. However, the use of visible light over 400 nm, which gives the lowest excited singlet state of the cationic dyes, caused no degradation. MB and TN were more efficient sensitizers for the degradation of NaHA than rose bengal (RB), although RB is a more efficient singlet oxygen (1O2) sensitizer than the cationic dyes. Under similar conditions the polysaccharides with carboxyl groups, such as alginic acid and polygalacturonic acid, also photodecomposed. However, the polysaccharides without carboxyl groups, such as pullulan and methyl cellulose, did not. The irradiation of the polysaccharides in the presence of powdered titanium dioxide as a photocatalyst to generate the hydroxyl radical (.OH) in aerated aqueous solution caused the fragmentation of all the polymers. It was confirmed that methyl viologen, an electron-accepting sensitizer, formed a charge-transfer complex with NaHA, the irradiation of which caused the efficient degradation of NaHA. In the presence of beta- and gamma-cyclodextrins the MB- and TN-sensitized photodegradation of NaHA was markedly suppressed. This was probably due to the formation of the inclusion complexes comprising the cationic dyes and the cyclodextrins. On the basis of the results obtained we propose that the cationic dye-sensitized degradation of NaHA involves a photoinduced electron-transfer process between the upper excited dyes and the ground-state NaHA and that .OH and 1O2 do not participate in the degradation.     

Synthesis of highly active visible-light-driven colloidal silver orthophosphate

The present study deals with the synthesis of highly uniform and spherical visible-light-driven colloidal silver phosphate (Ag₃PO₄) with the size of ～200 nm. These colloidal particles showed excellent photocatalytic activity for the removal of different dyes and pesticide under sunlight-type excitation. The photocatalytic activity of these particles, obtained by colloidal method, was found to be much higher than silver phosphate obtained by precipitation method, or titanium dioxide, or zinc oxide under identical conditions. The effect of catalyst amount and recyclability on the photocatalytic response of Ag₃PO₄ was also investigated.