TiO2的低温制备及其对有毒有机污染物的降解

溶胶水热法制备了TiO₂粉末,用X射线衍射仪(XRD)、比表面积及孔径分析仪(BET)和透射电镜(TEM)对TiO₂进行了初步表征,结果显示:纳米TiO₂主要为锐钛矿相(含板钛矿相(121)),比表面积为106.2 m²/g.在紫外光(λ≤387 nm)照射条件下,以有机染料罗丹明B(Rhodamine B,RhB)和无色小分子2,4-二氯苯酚(2,4-dichlorophenol,2,4-DCP)的紫外光(λ≤387 nm)光催化降解试验为探针反应,低温(50℃)下制备的TiO₂粉末具有较高光催化活性,对RhB和2,4-DCP有较好的降解效果.通过分析紫外-可见光谱(UV-Vis)、红外光谱(FTIR)和总有机碳(TOC)测定,发现TiO₂/UV体系能使RhB和2,4-DCP发生有效的降解,反应5 h后RhB和7 h后2,4-DCP的矿化率分别达到81.2%和86.8%.同时,采用辣根过氧化物酶(POD)、N,N-二乙基对苯二胺(DPD)分光光度法和苯甲酸荧光光度法分别测定了在降解过程中H₂O₂和羟基自由基(.OH)的变化,表明TiO₂光催化机理涉及到.OH历程.     

Fabrication of urchin‐like Ag/ZnO hierarchical nano/microstructures based on galvanic replacement mechanism and their enhanced photocatalytic properties

Urchin‐like Ag/ZnO hierarchical nano/microstructures have been synthesized through a facile low‐temperature hydrothermal growth method based on galvanic replacement mechanism. The experimental results show that the urchin‐like Ag/ZnO heterostructures are formed through the epitaxial growth of ZnO nanorods on the {111} facets of Ag nanoparticles along their own c‐axis. The photocatalytic properties of the products were evaluated by the degradation of RhB dye solution under ultraviolet irradiation, and the results show that the products exhibit significantly enhanced photocatalytic properties comparing with pure ZnO nanorods. The products with a Ag content of 35.64 atom % prepared with a Ag⁺ concentration in solution of 5 mM exhibit surprisingly high degradation rate (99.5%) for RhB dye solution (4 mg/L) after photocatalytic reaction for only 14 min under ultraviolet irradiation. The Schottky barrier formed at the metal‐semiconductor interfaces improves the segregation of charges and prevents the charge recombination, and thus significantly enhances the photocatalytic activities of the products. On the other hand, the high stability of the urchin‐like Ag/ZnO hierarchical nano/microstructures can effectively prevent the aggregation of nanostructures with simultaneously preserving high photocatalytic properties due to the existence of nanosized unites. Copyright © 2016 John Wiley & Sons, Ltd.     

紫外光下纳米TiO2 薄膜亲水性机理的电化学研究

The nanometer films of TiO2 were prepared by sol-gel method on ITO（Indium-tin oxide,SnO2:In） substrate. The TiO2 film was the anatase phase with a particle size of 100 nm from the measurements of X-ray diffraction and AFM（Atomic-Force-Microscope）. Electrochemical characteristics of ITO/ TiO2 electrode under UV（ultraviolet）irradiation were investigated using the method of cyclic voltammetry. A new oxidative peak was observed at 0.035 V when the TiO2 electrode was irradiated by 253.7 nm UV light for a certain time. The peak current increased with the irradiation time. It was assumed that the new oxidative peak resulted from Ti3+,which was formed during the UV illumination. The changes of hydrophilicity of the TiO2 thin film on ITO under UV light were also observed. It was assumed that the changes of hydrophilicity of the films may be related with the formation of Ti3+ on the surface when the film was irradiated by UV light.     

Cu2+/TiO2对甲基橙的光催化降解机理

以自制的掺铜离子的混晶型二氧化钛为光催化剂,考察了甲基橙光催化降解过程中pH值和光源的影响,提出了两种不同的光催化降解机理:在高压汞灯照射下,TiO2的价带电子被激发到导带,光生电子和空穴主要通过Cu2+ 的短路循环而复合,光催化剂的活性降低;在太阳光照射下,甲基橙发生自身光敏化氧化反应,受激电子从单线态或三线态的甲基橙分子跃迁到TiO2的导带,Cu2+起到电荷传递中继站的作用,加速了注入电子向H2O2的转移,从而促进了甲基橙的光催化降解。     

TiO_2薄膜光催化降解亚甲基蓝(英文)

用常压气相沉积法镀膜制得的二氧化钛薄膜为催化剂,以紫外灯为光源,研究了亚甲基蓝的光催化降解。实验表明：镀膜时基片温度为２００℃;用铜线作为底物,在染料溶液中加Ｈ２Ｏ２,可提高光催化活性。     

Hydrothermal synthesis, structure and photocatalytic property of nano-TiO_2-MnO_2

TiCI4 and MnSO4.H2O as raw materials are hydrolyzed stiochiometrically, following the intermediate of oxide hydrating reacts at 150℃, 0.5 MPa in high-pressure reactor, after filtering, washing and drying, nanometric TiO2-MnO2 (Ti1-xMnxO2) is prepared. The effects of the reaction temperature and time on nanometric TiO2-MnO2 are also discussed. XRD shows that the product is TiO2-MnO2 with amorphous phase. After being sintered at above 780℃, it transfers into Ti1-xMnxO2 with a rutile structure. TEM shows that TiO2-MnO2 is the spherical particle. And the average diameter of the particles is 20 nm. The optical absorbance was determined by UV-265 spec-trophotometer after dispersing the sample in the mixture of water and glycerol with the ratio of 1 : 1 equably. It is found that the nano-material possesses the advantages of both nano-TiO2 and nano-MnO2, and it has strong absorption in the UV and visible region. Photodegradation of dyes in an aqueous solution is investigated using nanometricTiO2-MnO2 as a pho     

TiO2/斜发沸石光催化降解罗丹明B的研究

制备了一系列TiO₂/斜发沸石催化剂(不同焙烧温度、不同粒度和不同负载量),它们在紫外光照射下可降解有机染料罗丹明B(RhB).发现焙烧温度为500℃、粒度为180—200目、TiO₂实际质量分数为6.18%的催化剂样品活性较好.将其与P25对比,发现其降解速率虽低于P25(紫外光照84 min,P25COD变化率为100%,而焙烧温度为500℃的TiO₂/斜发沸石催化剂经紫外光照5.5 h,COD变化率为71.8%),但是TiO₂/沸石催化剂易于回收再利用,而纯P25因为颗粒细小,沉降速率慢,而不能快速分离.用XRD、TEM、BET、TG-DTA和紫外可见漫反射等方法表征了这些催化剂,结果表明催化剂比表面积增大有利于催化活性的提高.     

内嵌硫化镉与上转换纳米颗粒的二氧化钛复合纳米管用于近红外光驱动光催化

由于近红外光在太阳光谱中占44%,因此,近红外光驱动的光催化剂的研制具有十分重要的意义.上转换发光材料可将低能量的近红外光子转换为高能光子,这种高能光子可以通过构建荧光共振转移系统将能量转移并活化量子效率较高的半导体材料,对于太阳能的转化利用具有潜在的应用前景.在本文中,通过胶体化学的过程在电纺丝制备的内嵌CdS纳米颗粒以及上转换荧光纳米颗粒(UCNPs)的二氧化硅复合纳米纤维表面外延生长一层二氧化钛层,通过高温煅烧得到二氧化钛复合纳米管.我们通过二氧化硅结构将CdS纳米颗粒与上转换荧光纳米颗粒紧紧束缚在一起,实现较高的荧光共振能量转移.而且,选择β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)作为纳米能量转换器,替代以前研究工作中使用的β-NaYF4:Yb(30%),Tm(0.5%)或者β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4纳米颗粒,来进一步提高近红外光的转换效率.通过透射电子显微镜照片很清楚的观察到制备的TiO2复合纳米管内部内嵌有大量的CdS与上转换纳米颗粒.通过X-射线衍射以及X-射线光电子能谱能仪器对产物的物相以及表面的化学组成进行了细致的表征.结果显示,通过本实验方法已经成功获得了TiO2复合纳米管.用稳态与瞬态荧光仪研究了最终样品的荧光性质.研究结果揭示,与上转换纳米颗粒以及二氧化硅复合纳米纤维相比,复合二氧化钛纳米管可以将上转换荧光纳米颗粒的(UV-Vis)部分荧光完全淬灭了.特别是,铒离子的荧光(650 nm)也被有效淬灭转移,说明本研究采用β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米能量转换器,可以提高近红外光的转换效率,紫外-可见吸收光谱证实,这种二氧化钛纳米管在紫外-可见光区中的吸收光谱与β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米颗粒的荧光光谱具有较大的重叠,使得上转换荧光纳米颗粒与CdS以及二氧化钛组分之间的荧光共振转移的效率大大提高,进而会显著提高光催化的效果.以罗丹明染料作为污染物为模型,我们研究了罗丹明染料在氙灯下或者近红外光光照下的光催化分解实验.研究结果表明,90%的罗丹明染料分子在20 min内就被降解掉,效率高于其它的近红外光催化剂.上转换荧光纳米颗粒的能量转换效率可以得到大幅度提高,本研究工作中制备的光催化剂利用太阳能的效率将会得到极大提高,在未来为能源危机以及环境保护提供一种可供选择的方法与技术.     

超临界流体干燥法制备TiO2／C纳米粒子及光催化性能

以TiCl4为原料,采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO2/C复合光催化剂.以苯酚的光催化降解对所得催化剂的催化活性进行了评价.结果表明,纳米TiO2/C复合粒子与单组分TiO2比较,复合粒子光催化活性高于单组分的TiO2,h苯酚降解率高达975 ％,COD为957%.并用XRD、TEM、 UV-Vis和XPS等手段进行了表征,iO2以锐钛矿型形式存在.比较了不同制备方法制得的TiO2/C复合催化剂,得出超临界干燥法制备的光催化剂具有粒径小,比表面积大,分散性好,光催化活性高等特点.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料, 与葡萄糖溶液在220 ℃下进行水热反应, 再在空气中520 ℃焙烧, 制备出介孔TiO2. 用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征. 结果表明, 该介孔TiO2具有微米级棒状或针状形貌, 晶粒大小为12.3 nm, 比表面积为106 m2·g-1, 孔容为0.31 cm3·g-1, 孔径为8.06 nm, 焙烧处理后晶型仍是锐钛矿相. 水热生成的碳抑制了晶粒的团聚生长和晶型的转变, 提高了介孔TiO2的热稳定性. 甲基橙降解实验评价了介孔TiO2的光催化性能, 结果发现其活性与商用TiO2催化剂P25相当, 而其较大的粒径更容易回收再利用. 以碘化钾为探针反应, 表明介孔TiO2的光催化机制以光生空穴氧化为主.