State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, PR China.
Chemistry. 2013 Feb 11;19(7):2433-41. doi: 10.1002/chem.201202778. Epub 2013 Jan 7.
Exploiting advanced photocatalysts under visible light is of primary significance for the development of environmentally relevant photocatalytic decontamination processes. In this study, the ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate, was employed for the first time as both a structure-directing agent and a dopant for the synthesis of novel fluorinated B/C-codoped anatase TiO(2) nanocrystals (T(IL)) through hydrothermal hydrolysis of tetrabutyl titanate. These T(IL) nanocrystals feature uniform crystallite and pore sizes and are stable with respect to phase transitions, crystal ripening, and pore collapse upon calcination treatment. More significantly, these nanocrystals possess abundant localized states and strong visible-light absorption in a wide range of wavelengths. Because of synergic interactions between titania and codopants, the calcined T(IL) samples exhibited high visible-light photocatalytic activity in the presence of oxidizing Rhodamine B (RhB). In particular, 300 °C-calcined T(IL) was most photocatalytically active; its activity was much higher than that of TiO(1.98)N(0.02) and reference samples (T(W)) obtained under identical conditions in the absence of ionic liquid. Furthermore, the possible photocatalytic oxidation mechanism and the active species involved in the RhB degradation photocatalyzed by the T(IL) samples were primarily investigated experimentally by using different scavengers. It was found that both holes and electrons, as well as their derived active species, such as (·)OH, contributed to the RhB degradation occurring on the fluorinated B/C-codoped TiO(2) photocatalyst, in terms of both the photocatalytic reaction dynamics and the reaction pathway. The synthesis of the aforementioned novel photocatalyst and the identification of specific active species involved in the photodegradation of dyes could shed new light on the design and synthesis of semiconductor materials with enhanced photocatalytic activity towards organic pollutants.
在可见光下开发先进的光催化剂对于开发与环境相关的光催化净化过程至关重要。在这项研究中,离子液体(IL)1-丁基-3-甲基咪唑四氟硼酸盐首次被用作结构导向剂和掺杂剂,通过四丁基钛酸酯的水热水解合成新型氟代 B/C 共掺杂锐钛矿 TiO(2)纳米晶(T(IL))。这些 T(IL)纳米晶具有均匀的晶粒和孔径,并且在煅烧处理时对相转变、晶体熟化和孔坍塌具有稳定性。更重要的是,这些纳米晶具有丰富的局域态和在宽波长范围内的强可见光吸收。由于钛和共掺杂剂之间的协同相互作用,煅烧后的 T(IL)样品在存在氧化罗丹明 B(RhB)的情况下表现出高可见光光催化活性。特别是,300°C 煅烧的 T(IL)具有最高的光催化活性;其活性远高于在相同条件下没有离子液体的 TiO(1.98)N(0.02)和参考样品(T(W))。此外,通过使用不同的清除剂,实验上主要研究了 T(IL)样品光催化氧化 RhB 的可能的光催化氧化机制和涉及的活性物质。结果发现,空穴和电子以及它们衍生的活性物质(如(·)OH)都有助于氟代 B/C 共掺杂 TiO(2)光催化剂上 RhB 的降解,这是基于光催化反应动力学和反应途径。上述新型光催化剂的合成以及参与染料光降解的特定活性物质的鉴定为设计和合成具有增强的对有机污染物的光催化活性的半导体材料提供了新的思路。