应用化学 ›› 2010, Vol. 27 ›› Issue (12): 1413-1418.DOI: 10.3724/SP.J.1095.2010.00038

• 研究论文 • 上一篇    下一篇

TiO2-yNx纳米光催化剂的制备及其可见光响应机理

王城英,姜洪泉*,李井申,卢智宇,闫盼盼   

  1. (哈尔滨师范大学化学化工学院 哈尔滨 150500)
  • 收稿日期:2010-01-18 修回日期:2010-03-22 出版日期:2010-12-10 发布日期:2010-12-10
  • 通讯作者: 姜洪泉,男,教授; E-mail:h.q.jiang1119@163.com; 研究方向:环境功能纳米材料的制备及应用技术
  • 基金资助:
    黑龙江省教育厅科学技术研究项目(11551115),哈尔滨师范大学青年学术骨干资助计划项目(08XBSK89)

Preparation and Visible-light Responsive Mechanism of Nanoscale TiO2-yNx Photocatalyst

WANG Cheng-Ying, JIANG Hong-Quan*, LI Jing-Shen, LU Zhi-Yu, YAN Pan-Pan   

  1. (School of Chemistry and Chemical Engineering,Harbin Normal University,Harbin 150500)
  • Received:2010-01-18 Revised:2010-03-22 Published:2010-12-10 Online:2010-12-10
  • Contact: Jiang HongQuan

摘要:

利用溶胶-凝胶技术,以尿素为氮源,采用原位掺杂方式制备了TiO2-yNx纳米粉体;以亚甲基蓝(MB)溶液在可见光下的光催化降解评价其可见光催化活性;考察了体系初始pH值、N的掺杂量和焙烧温度对样品可见光催化活性的影响。 结合XRD、XPS、ESR和DRS测试技术,研究了N掺杂纳米TiO2的可见光响应机理。 研究结果表明,TiO2-yNx纳米粉体的优化制备工艺条件为:体系初始pH=0.52,掺杂比n(N)∶n(Ti)=1∶6,焙烧温度为440 ℃。 此条件下制备的样品N含量为0.77%,为单一的锐钛矿相,平均粒径为19.0 nm,具有良好的可见光催化活性。 N掺杂导致TiO2纳米粉体的表面羟基含量增加,形成了大量束缚单电子的氧空位;N取代晶格O形成了N—Ti—O和O—N—Ti键合结构。 N掺杂导致TiO2纳米粒子的吸收带边红移,对可见光的吸收能力明显增强,这表明N掺杂改变TiO2电子结构,使带隙窄化,降低光响应阈值。 N掺杂TiO2纳米粒子的可见光响应归因于N取代掺杂形成的掺杂能级与氧空位形成的缺陷能级共同作用所致。

关键词: 纳米TiO2, 氮掺杂, 溶胶-凝胶, 可见光响应, 光催化

Abstract:

TiO2-yNx nanoparticles were prepared by in situ doping sol-gel method using urea as the nitrogen source. Their visible-light photocatalytic activity was evaluated by the photocatalytic degradation of methylene blue(MB) in an aqueous solution under visible-light irradiation. The effects of original pH value, nitrogendoping content and calcination temperature on the as-prepared samples were investigated. The visible-light responsive mechanism of the N-doped sample was studied by means of XRD, XPS, ESR and DRS. The results show that the optimal conditions for the preparation of TiO2-yNx nano-particles are as follows: original pH value 0.52, doping proportion of n(N) to n(Ti) 1∶6, and calcination temperature 440 ℃. The as-prepared sample of single anatase phase with 0.77% N atoms and with average crystal size 19.0 nm exhibits a good visible-light photocatalytic activity. N-doping leads to increasing the surface hydroxyl groups and forming abundant surface oxygen vacancies bounding single-electrons. The O atoms in the TiO2 lattice are substituted by the doped N atoms so that form the N—Ti—O and O—N—Ti bonding structures. N-doping results in a remarkable red-shift of the TiO2 absorption band-edge and significantly increases the absorption of visible-light. The results indicate that N-doping changes the electronic structure of TiO2 and decreases the band-gap. The visible-light response of the N-doped sample is ascribed to a synergetic effect of impurity and defect energy levels that are originated from the substitutional N-doping and the formation of oxygen vacancies accordingly.

Key words: nano titania, N-doping, sol-gel, visible-light response, photocatalysis

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