贵金属修饰的Ti O2空心纳米光催化材料由于具有大的比表面积、低的质量密度、良好的表面渗透性、强的光吸收能力以及界面电荷的快速转移,因而表现出优异的光催化性能.为了制备结构可控且精良的贵金属修饰Ti O2空心纳米光催化材料,人们先后采用湿化学法、高温固相法、声化学法及光化学沉积法等.由于在制备过程中涉及多种异相材料的合成和结构控制,因此上述合成方法通常需要复杂且多步过程(有些过程甚至很容易导致结构破坏),从而限制了其在光催化领域的实际应用.本文开发了一种简单的模板诱导法,成功制备了Ag纳米粒子修饰的Ti O2空心八面体光催化剂.合成过程包括模板指导沉积和原位模板溶解.以Ag2O八面体为模板,TiF 4水溶液为前驱体,首先通过Ti F4水解形成Ti O2纳米粒子沉积在Ag2O模板表面,而Ti F4水解产生的酸性HF水溶液可原位溶解碱性的Ag2O模板,从而一步制得Ti O2空心八面体.同时,利用Ag2O以及Ag+离子的光敏特性,在光照条件下使Ag2O和Ag+离子生成Ag纳米颗粒,直接沉积在Ti O2空心八面体的内外表面,得到Ag/Ti O2光催化剂.由此可见,该合成方法具有明显的步骤少的优点.扫描电镜、透射电镜、能量散射和紫外-可见光谱等表征结果表明成功制得内外Ag纳米粒子修饰的Ti O2空心八面体光催化剂,其中TiO 2空心八面体的壁厚约为25 nm,边长约为1μm,而修饰在其表面的Ag纳米粒子尺寸仅为5–10 nm.此外,通过控制Ti F4前驱体浓度,还可制备核壳结构的Ag2O@Ti O2八面体以及不同壁厚Ag修饰的Ti O2空心八面体,表明该方法在Ag/Ti O2形貌合成上的多样性和可控性.为了获得良好的光催化活性,对制备的Ag纳米粒子修饰的Ti O2空心八面体光催化剂进行了不同温度的热处理.X射线衍射结果表明,即使在600 oC高温下,制备的Ag/Ti O2空心八面体光催化剂依然能够保持原有的特殊?
Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area,low density,good surface permeability,strong light-harvesting capacity,and rapid interfacial charge transfer. However,the present preparation methods usually include complicated and multistep procedures,which can cause damage to the hollow nanostructures. In this paper,a facile template-induced synthesis,based on a template-directed deposition and in situ template-sacrificial dissolution,was employed to prepare Ag-modified TiO 2(Ag/TiO 2) hollow octahedra using Ag2 O octahedra as templates and TiF 4 as the precursor. In the synthetic strategy,the shells of TiO 2 hollow octahedra were formed by coating TiO 2 nanoparticles on the surface of Ag2 O templates based on the template-directed deposition. Simultaneously,the Ag2 O templates can be in situ removed by dissolving the Ag2 O octahedral template in HF solution produced via the hydrolysis reaction of TiF 4 in the reaction system. In addition,Ag nanoparticles were deposited on the inside and outside surfaces of TiO 2 shells by effectively using the photosensitive properties of Ag2 O and Ag+ ions under light irradiation,along with the formation of TiO 2 hollow octahedra. The Ag/TiO 2 hollow octahedra exhibited high photocatalytic activity because of their(1) short diffusion distances between photogenerated electrons and holes because of the thin shells of Ag/TiO 2 hollow octahedral,(2) deposition of Ag nanoparticles on the inside and outside surfaces of TiO 2 shells,and(3) rapid interfacial charge transfer between TiO 2 shells and Ag nanoparticles. This work may also provide new insights into preparing other Ag-modified and hollow nanostructured photocatalysts.