模板法制备三维有序氧化钛薄膜的结构调控

Structurally Tailored Three-Dimensional Ordered TiO_2 Films Fabricated by the Template Method

以聚苯乙烯微球胶体晶体为硬模板、四氯化钛为氧化钛前驱体,结合控制浸渍-煅烧工艺制备了三维有序TiO2薄膜材料,重点考察了浸渍液中TiCl4的浓度对最终TiO2薄膜样品结构的影响。利用X射线衍射(XRD)、热重分析(TGA)、扫描电子显微镜(SEM)、能谱仪(EDS)、透射电子显微镜(TEM)、选区电子衍射(SAED)和N2吸附/脱附等手段对样品的结构特征进行表征。XRD分析表明,经500℃煅烧2 h后所得样品为锐钛矿相TiO2;SEM结果显示,在本实验条件下随着前驱体溶液中TiCl4浓度的增大,TiO2薄膜的微观结构逐步由三维有序大孔TiO2(three-dimensional ordered macro-porous TiO2,3DOM-TiO2)演变为三维有序TiO2中空球(three-dimensional ordered TiO2hollow-spheres,3DOH-TiO2);TEM结果表明,3DOM-TiO2和3DOH-TiO2薄膜样品骨架由氧化钛纳米颗粒组成,大孔孔壁和中空球壳壁上存在由TiO2纳米颗粒堆积形成的不规则介孔。

With the polystyrene microspheres colloidal crystals as the hard templates and titanium tetrachloride as the TiO2 precursor, the three-dimensional ordered TiO2 films were synthesized by the controlled dipping-calcination method. The effects of the TICl4 concentrations in the precursor solution on the structures of the obtained TiO2 films were mainly investigated. The structure characteristics of the samples were characterized by X-ray diffraction （XRD）, thermogravimetric analysis （TGA）, scanning electron microscopy （SEM）, electron energy dispersive spectroscopy （EDS）, transmission electron microscopy （TEM）, selected area electron diffraction （SAED） and nitrogen adsorption-desorption techniques. The XRD results show that the obtained samples are anatase TiO2 after calcination at 500 ~C for 2 h. The SEM results indicate that with the increase of the TIC14 concentrations in the precursor solution, the microstructures of the TiO2 films are transformed from three-dimensional ordered macro-porous TiO2 （3DOM-TiO2） to three-dimensional ordered TiO2 hollow-spheres （3DOH-TiO2）. The TEM results show that the frameworks of the 3DOM-TiO2 and 3DOH-TiO2 films are composed of TiO2 nanoparticles, and there are the irregular mesoporous composed by TiO2 nanoparticles on the walls of the macropores and the shells of the hollow-spheres.