多孔TiO2薄膜自洁净玻璃的亲水性和光催化活性

亲水性多孔TiO2薄膜自洁净玻璃以含聚乙二醇的钛醇盐溶胶前驱体中通过浸渍提拉法制备;随着前驱物中聚乙二醇加入量的增加, 多孔TiO2薄膜表面的羟基含量也增加, 薄膜表面的亲水性增强, 水与薄膜表面的接触角下降为0°. 该亲水性多孔TiO2薄膜自洁净玻璃具有明显的自洁净和易清洗功能. 紫外-可见光透过光谱分析表明, 随着TiO2薄膜中孔径的增大, 光的散射增强, 透光率减小. 该TiO2镀膜玻璃对于紫外线具有吸收作用. 甲基橙水溶液的光催化降解实验表明, 在TiO2薄膜中引入适当大小的微孔可显著增强薄膜的光催化活性, 但当孔径接近400 nm时, 薄膜的光催化活性减弱.     

不锈钢金属丝网上TiO2纳米薄膜光催化剂的研究

以钛酸正丁酯为原料,采用溶胶-凝胶法在金属丝网上制备了TiO2薄膜光催化剂.利用SEM,TEM,AES和Raman光谱研究了薄膜的表面及结构特性.以甲醛的光催化氧化反应为试验反应,考察了提拉次数、PEG浓度和焙烧温度对TiO2薄膜光催化剂活性的影响.将TiO2薄膜的结构特性与其光催化活性进行了关联.结果表明,在前驱体溶胶中加入10%PEG400,提拉3次并于400℃下焙烧可制得具有中孔结构和结晶完好的锐钛矿型TiO2薄膜,并具有最佳的光催化活性.     

TiO_2/SiO_2纳米薄膜的光催化活性和亲水性

通过 sol-gel工艺在钠钙玻璃表面制备了均匀透明的 TiO2/SiO2复合纳米薄膜 .实验结果表明 : 当 SiO2添加量较高时 , TiO2/SiO2复合纳米薄膜的光催化活性明显降低 ;当 SiO2添加量较低时 ,TiO2/SiO2复合薄膜的光催化活性无明显变化 .在 TiO2薄膜中添加 SiO2,可以抑制薄膜中 TiO2晶粒的长大 ,同时薄膜表面的羟基含量增加 , 水在复合薄膜表面的润湿角下降 , 亲水能力增强 .当 SiO2含量为 10％－ 20％（摩尔分数）时获得了润湿角为 0°的超亲水性薄膜 .     

铝基板的界面扩散对薄膜型TiO2光催化活性的影响

以钛酸四丁酯为前驱体, 采用溶胶-凝胶法在铝基板表面制备了纳米晶TiO2薄膜. 运用XRD、SEM和XPS对制得的薄膜进行表征, 并测试了薄膜光催化降解亚甲基蓝(MB)的活性. 结果表明, TiO2薄膜样品在450 ℃焙烧30 min后, 晶粒排列比较致密, 粒径为10-20 nm, 并与铝基板紧密结合; 薄膜与铝基板发生了明显的界面扩散, 薄膜中的Al元素来自铝基板的界面扩散, 且界面层很宽, 扩散层厚度约为75 nm; 界面扩散的发生直接导致了TiO2薄膜的光催化活性下降. 但随着薄膜厚度增加, 铝基板对TiO2薄膜降解亚甲基蓝催化活性的影响不断减小.     

TiO2/SiO2纳米薄膜的光催化活性和亲水性

通过sol gel工艺在钠钙玻璃表面制备了均匀透明的TiO2/SiO2复合纳米薄膜.实验结 果表明: 当SiO2添加量较高时, TiO2/SiO2复合纳米薄膜的光催化活性明显降低;当SiO2添加 量较低时,TiO2/SiO2复合薄膜的光催化活性无明显变化.在TiO2薄膜中添加SiO2,可以抑制薄 膜中TiO2晶粒的长大,同时薄膜表面的羟基含量增加, 水在复合薄膜表面的润湿角下降, 亲 水能力增强.当SiO2含量为10％－20％（摩尔分数）时获得了润湿角为0°的超亲水性薄膜.     

Fe掺杂对纳米TiO2薄膜的结构与光催化性能的影响

采用溶胶-凝胶法制备了Fe掺杂的TiO2薄膜,利用X射线光电子能谱、X射线衍射技术、显微共聚焦拉曼光谱、紫外可见光谱和原子力显微镜等对薄膜进行表征,以甲基橙为反应模型对光催化活性进行测试。 结果表明,在300~600 ℃焙烧时,TiO2以锐钛矿结构存在,700 ℃焙烧时出现金红石结构。 随掺铁量和焙烧温度的增加,Fe/TiO2薄膜的表面粗糙度和晶粒尺寸均逐渐增大;随镀膜层数的增加,Fe/TiO2薄膜光谱吸收向可见光方向移动;较低含量的铁掺杂改善了TiO2薄膜的光催化活性,而较高含量的铁掺杂则使TiO2薄膜的光催化活性下降,掺铁量为0.1%时Fe/TiO2薄膜的光催化活性最好。     

Au/TiO2薄膜的制备及其光催化氧化对硝基苯酚的性能

 采用溶胶-凝胶法制备了掺杂Au的TiO2薄膜,考察了其光催化氧化对硝基苯酚的活性,并采用原子力显微镜、 X射线光电子能谱、热重-差示量热扫描和X射线衍射技术对薄膜进行了表征. 结果表明, Au/TiO2薄膜主要含有Ti, O, Au和C元素,其中Au主要以0价形式存在. 经高温焙烧后薄膜中的Au向表面聚集,随着焙烧温度的升高,薄膜表面逐渐变得粗糙,颗粒逐渐变大,薄膜的光催化活性下降. 与纯TiO2薄膜相比,掺杂Au的TiO2薄膜的光催化活性有所提高, 在673 K下焙烧的Au/TiO2薄膜的光催化活性较好,反应1 h后对硝基苯酚的降解率可以达到51.4%.     

后处理对TiO_2纳米薄膜的表面结构和光催化活性的影响

半导体TiO2光催化材料对环境中各种污染物的明显去除效果已引起人们的广泛关注犤1～6犦。在普通钠钙玻璃表面涂制高光催化活性的TiO2纳米薄膜,制成环保建筑材料,不仅可以自洁玻璃表面,而且可以用于净化空气、处理废水等。但由于在热处理过程中玻璃基体内的Na+离子扩散到薄膜表面,形成光生电子和空穴的复合中心,使TiO2纳米薄膜的光催化活性大大降低犤7～10犦。为了减少玻璃中Na+离子对TiO2薄膜光催化活性的有害影响,Paz等犤8犦研究了将钠钙玻璃浸入酸溶液中,使玻璃表面的钠离子被酸中的氢离子置换出来;在玻璃表面形成SiO2凝胶层,以便阻…     

氟掺杂纳米 TiO2 薄膜的低温制备及其光催化性能

 以氟化铵为氟源, 采用水热法制得氟掺杂 TiO2 (FTO) 溶胶, 并通过浸渍提拉法在低温下制备了 FTO 薄膜. 其中在 120 oC 下水热处理 10 h 所得的 TiO2 溶胶制备的薄膜均匀透明, 具有较高的光催化活性. 氟掺杂后的 TiO2 晶粒尺寸并未发生明显变化, 但薄膜的光催化活性显著升高. F/Ti 摩尔比为 0.01 时, FTO 薄膜的光催化活性最高, 比 TiO2 薄膜的活性升高了 23%. X 射线光电子能谱结果表明, 氟掺杂 TiO2 中的氟离子存在晶格取代掺杂和表面化学吸附两种形式. 这两种氟离子的共同作用是 FTO 薄膜光催化活性升高的主要原因.     

液相沉积法制备光催化活性掺铁TiO2薄膜

 通过在氟钛酸铵－氟铁酸混合溶液中加入硼酸溶液，应用液相沉积法制备了具有高光催化活性的掺铁TiO2薄膜．用ICP－AES测定了掺铁TiO2薄膜中Fe3＋的浓度，用XRD，AFM，UV－Vis和阶梯仪等对TiO2薄膜的沉积条件、结构、膜厚和性能进行了表征，并以亚甲蓝降解反应评价了掺铁TiO2薄膜的光催化活性．结果表明，在硼酸／六氟钛酸铵摩尔比为2～4时，掺铁TiO2薄膜中含有锐钛矿相TiO2．当掺Fe3＋浓度为0．05％，热处理温度为300℃时，掺铁TiO2薄膜具有最高的光催化活性，其光催化活性是未经热处理时的3．9倍，是经300℃热处理但未掺铁TiO2薄膜的1．4倍．     

TiO2 Thin Film with Varied Porous Structure Applied on the Degradation of Methylene Blue

In this study, porous TiO₂ thin films were prepared by the sol‐gel method employing polyethylene glycol 1000 (PEG 1000) as an organic template. Pore sizes were adjusted by varying the concentration of PEG 1000. The optimal PEG concentration range required to form TiO₂ films with a regular porous structure was investigated and was found to be 0.01–0.015 M. As the PEG 1000 concentration increased, the surface of these films became rougher because of larger pores. Degradation of methylene blue (MB) under UV irradiation was used to determine the photocatalytic activity of the films. In addition, the effect of the pH value of the MB solution on the films was evaluated by controlling its pH value at 5, 7, and 9. The results showed that the photocatalytic activity was correlated to the pore size and pore density of the thin films. TiO2 thin films possessing pore sizes in the diameter range of 35–85 nm exhibited the best conversion of 98% after 8 h of UV irradiation when the pH value was 7.     

Atomic Force Microscopic Studies of Porous TiO2 Thin Films Prepared by the Sol-Gel Method

Porous titanium dioxide thin films were prepared from alkoxide solutions with and without polyethylene glycol (PEG) by the sol-gel method on soda-lime glass. The effects of PEG addition to the precursor solution on the microstructure and roughness of the resultant thin films were investigated by atomic force microscopy (AFM). It was found that TiO₂ films prepared from the precursor solution without PEG had granular microstructure and flat texture, and was composed of about 100 nm spherical particles. With an increase in the times of coating cycles, the roughness of films decreased and the size of TiO₂ particles increased. On the other hand, the larger the amount and molecular weight of the added PEG in precursor solutions, the larger the diameter and the depth of pores in the resultant films on the decomposition of PEG during heat-treatment. The surface of the films was also rougher, and fewer pores were produced during heat-treatment. The mechanism of porous structure formation in the TiO₂ films was explained using the principle of spinodal phase separation.     

Preparation,Microstructure and Photocatalytic Activity of the Porous TiO2 Anatase Coating by Sol-Gel Processing

In this study the porous TiO² anatase coatings are prepared from alkoxide solutions containing polyethylene glycol (PEG) by a dip-coating technique. The effects of PEG addition to the precursor solution on the photocatalytic activity and microstructure of the resultant coatings are studied. The larger amount and the larger molecular weight of PEG, the larger size and more pores produced in the resultant coatings on the decomposition of PEG during heat-treatment. The adsorbed hydroxyl content of such porous coatings is found to increase due to the larger size and more pores in the coatings. However, the transmittance of the coatings decreases due to the scattering by the larger size and more pores. Photocatalytic degradation experiments show that organophosphorous insecticide, dimethyl-2,2-dichlorovinyl phosphate (DDVP), was efficiently degraded in the presence of the porous TiO₂ coatings by exposing the DDVP solution to sunlight. Photocatalytic degradation rate was related to the adsorbed hydroxyl content, transmittance and morphology of the resultant coatings.     

Formation of nanoporous poly(aryl amide ether) (PAAE) films by selective removal of poly(ethylene glycol) (PEG) from PEG/PAAE composite films

Poly(aryl amide ether) (PAAE) thin films with nanometer-sized pores have been prepared in two steps: (1) solution casting of partially miscible poly(ethylene glycol) (PEG)/PAAE blends from one of their common solvents, dimethyl sulfoxide (DMSO), results in formation of PEG/PAAE nanocomposite films; (2) selective removal of PEG component by water washing yields nanosized, porous PAAE films. The pores have been found to have a small size variation and cover the whole surface homogeneously. With an increase in PEG contents, the sizes of the pores increase but the size distributions do not have much changes. This has been ascribed to formation of small PEG domains in PEG/PAAE composite films, which is facilitated by the strong interactions, mostly hydrogen bonds, between PEG and PAAE macromolecular chains.     

Preillumination of TiO2 and Ta2O5 photoactive thin films as a tool to tailor the synthesis of composite materials

Illumination of TiO 2 thin films with UV light is known to induce the transformation of the surface of this material from partially hydrophobic into fully hydrophilic. The present work shows that this transformation is accompanied by other effects that may be used to control the synthesis of composite materials. For this purpose, TiO 2 and Ta 2O 5 transparent thin films with a columnar structure and open pores were prepared by electron evaporation at glancing angles. Transparent TiO 2 thin films with micropores (i.e., pores smaller than 2 nm) prepared by plasma enhanced chemical vapor deposition (PECVD) were also used. All these films became hydrophilic upon UV illumination. Rhodamine 6G and Rhodamine 800 dyes were irreversibly adsorbed within the columns of the TiO 2 and Ta 2O 5 thin films by immersion into a water solution of these molecules. Isolated and aggregated molecules of these two dyes were detected by visible absorption spectroscopy. The infiltration adsorption efficiency was directly correlated with the acidity of the medium, increasing at basic pHs as expected from simple considerations based on the concepts of the point of zero charge (PZC) in colloidal oxides. The infiltration experiments were repeated with columnar TiO 2 and Ta 2O 5 thin films that were subjected to preillumination with UV light. It was found that this treatment produced a modification in the type (isolated or aggregated) and amount of dye molecules incorporated into the pores. Moreover, the selective adsorption of a given dye in preilluminated areas of the films permitted the lithographic coloring of the films. Preillumination also controls the UV induced deposition of silver on the surface of the microporous TiO 2 thin films. It was found that the size distribution of the formed silver nanoparticles was dependent on the preillumination treatment and that a well-resolved surface plasmon resonance at around 500 nm was only monitored in the preilluminated films. A model is proposed to account for the effects induced by UV preillumination on the TiO 2 and Ta 2O 5 oxide surfaces. The possibilities of this type of light treatment for the tailored synthesis of nanocomposite thin films (i.e., dye-oxide, metal nanoparticles-oxide) are highlighted.     

(Ni-Mo)/TiO2纳米薄膜光催化降解刚果红的性能与机理

用恒电流复合电沉积方法制备(Ni-Mo)/TiO2薄膜,以扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼(Raman)光谱和紫外-可见漫反射光谱(UV-VisDRS)对薄膜的表面形貌、晶相结构和光谱特性进行了表征,以刚果红为模拟污染物对薄膜的光催化性能进行了测定,并讨论了刚果红溶液的pH值对薄膜光催化活性的影响.采用循环伏安技术和向溶液中加入活性物种捕获剂的方法对薄膜光催化降解机理进行了探索.结果表明:(Ni-Mo)/TiO2薄膜是由粒径为50-100nmTiO2纳米粒子相和纳米晶Ni-Mo固溶体相构成的复合薄膜.薄膜具有较高的光催化活性,卤钨灯照射80min后,复合薄膜光催化刚果红的降解率是多孔TiO2(DegussaP25)/ITO(氧化铟锡)纳米薄膜的2.43倍.(Ni-Mo)/TiO2薄膜光催化活性的提高主要归因于薄膜层中有效形成的(Ni-Mo)/TiO2异质结和良好的电子通道,以及Ni-Mo纳米晶合金对溶解氧和激发电子还原反应的催化作用.分别给出了在紫外和可见光下薄膜光催化降解刚果红的反应机理.     

Novel guests for porous columnar thin films: the switchable perchlorinated trityl radical derivatives

TiO(2) and SiO(2) porous thin films consisting of tilted nanocolumns prepared by glancing angle evaporation (GLAD) have been infiltrated with guest derivatives belonging to the family of perchlorinated trityl radicals, novel guest molecules presenting an open-shell electronic configuration associated with paramagnetism, fluorescence, and electroactivity. The main driving forces for infiltration from aqueous solutions of the carboxylate-substituted radical derivatives are the electrostatic interactions between their negative charge and the net positive charges induced on the film pores. Positive charges on the internal surface of the films were induced by either adjusting the radical solution pH at values lower than the point of zero charge (PZC) of the oxide or passivating the nanocolumns oxide surface with a positively charged aminosilane. The infiltrated composite thin films are robust and easy to handle thanks to the physical protection exerted by the film columns. They also keep the multifunctionality of the used guests, as confirmed by electron paramagnetic resonance (EPR), UV-vis spectroscopy, and fluorescence spectroscopy. To prove the electroactivity of the infiltrated porous films, a porous TiO(2) host layer was supported onto conductive indium tin oxide (ITO). By application of an appropriate redox potential, the guest radical molecules have been reversibly switched from their open-shell electronic configuration to their diamagnetic state and hence changed their optical properties. On the basis of these results, it is herein proposed that the appropriate surface functionalization of the pore internal surface of GLAD thin films can be used to prepare novel radical-oxide composite thin films usable for the development of robust switchable electrically driven photonic and magnetic devices.     

Effect of pore size/distribution in TiO2 films on agarose gel electrolyte-based dye-sensitized solar cells

This study develops a simple method to change the distribution of the pore size in a TiO₂ layer, using polyethylene glycol (PEG), while maintaining nearly the same surface area and porosity to clarify how large pores affect the performance of dye-sensitized solar cells (DSSCs). Specifically, a heating step at 100 °C for a specific duration is added prior to PEG removal and TiO₂ sintering at 400 °C. This process transforms the role of the PEG from a surfactant to a pore generator (porogen) and forms larger pores, depending on the loading and aggregation time for the PEG to gain larger pores. The effect of larger pores in TiO₂ films under 30 % PEG loading, on the performance of an agarose gel electrolyte-based DSSC, was further investigated using the ionic liquid, 1-allyl-3-ethylimidazolium iodide (AEII). The I–V characteristic and the electrochemical impedance spectroscopy analysis show that larger pores readily improve redox couple diffusion in a TiO₂ porous electrode and modify the interface between electrolyte and TiO₂. Using the optimized TiO₂ film with larger pores (30 % PEG loading, 100 °C/60 min), an efficiency of 7.43 % is achieved for the agarose gel electrolyte-based DSSC, which represents a 26.1 % improvement over TiO₂ without the addition of PEG.     

The morphologies and optoelectronic properties of delafossite CuFeO2 thin films prepared by PEG assisted sol–gel method

Single phase delafossite CuFeO₂ thin films were synthesized by a simple sol–gel method. The influence of polyethylene glycol (PEG) on the morphology and optoelectronic properties of the films was studied by addition of 1.0 g PEG in 10 ml precursor solution. The crystal sizes of the derived CuFeO₂ films with and without addition of PEG were 49 nm, but the sample with addition of PEG (labeled as CFO-PEG) showed weaker c-axis orientation growth. The sample without addition of PEG (labeled as CFO) showed a compact surface without detectable pores and had a thickness around 50 nm. However, the sample CFO-PEG exhibited a porous surface with worm-like grains in nanometric scale and had a thickness around 310 nm. Enhanced absorbance in UV–vis region was observed for the sample CFO-PEG which might ascribe to both the thickness and porous surface. The optical direct bandgaps at near-UV were estimated to be ~3.0 and 3.38 eV for the sample CFO-PEG and CFO, respectively. Though the porous surface of CFO-PEG has improved the absorbance in UV–vis region, the resistivity has also been increased due to the homogeneous distribution of interspaces between the worm-like grains, which makes the incident photon to current efficiency of CFO-PEG lower than that of CFO.