不同浓度Sn4+离子掺杂TiO2的结构、性质和光催化活性

doi:10.3866/PKU.WHXB201303182

物理化学学报 >> 2013, Vol. 29 >> Issue (06): 1305-1312.doi: 10.3866/PKU.WHXB201303182

不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性

张鹏^1,2, 赵路松^1,2, 姚江宏^1,2, 曹亚安^1,2

1 南开大学物理科学学院, 天津 300071;
2 南开大学泰达应用物理学院, 弱光非线性光子学教育部重点实验室, 天津 300457

收稿日期:2012-12-11 修回日期:2013-03-18 发布日期:2013-05-17
通讯作者: 曹亚安 E-mail:caoyaan@yahoo.com
基金资助:
国家自然科学基金(51072082, 21173121, 11074129)和国家重点基础研究发展规划项目(973) (2012CB934201)资助

Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions

ZHANG Peng^1,2, ZHAO Lu Song^1,2, YAO Jiang Hong^1,2, CAO Ya An^1,2

1 College of Physics, Nankai University, Tianjin 300071, P. R. China;
2 Key Laboratory of Weak Light Nonlinear Photonics, Ministry of Education, Teda Applied Physics School, Nankai University, Tianjin 300457, P. R. China

Received:2012-12-11 Revised:2013-03-18 Published:2013-05-17
Supported by:
The project was supported by the National Natural Science Foundation of China (51072082, 21173121, 11074129) and National Key Basic Research Program of China (973) (2012CB934201).

摘要/Abstract

摘要：

采用溶胶-凝胶法制备出纯TiO₂和不同浓度Sn⁴⁺离子掺杂的TiO₂光催化剂(TiO₂-Snx%, x%代表Sn⁴⁺离子掺杂的TiO₂样品中Sn⁴⁺离子摩尔分数). 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)和表面光电压谱(SPS)确定了TiO₂-Snx%催化剂的晶相结构和能带结构, 结果表明: 当Sn⁴⁺离子浓度较低时, Sn⁴⁺离子进入TiO₂晶格, 取代并占据Ti⁴⁺离子的位置, 形成取代式掺杂结构(Ti_1-xSn_xO₂), 其掺杂能级在导带下0.38 eV处; 当Sn⁴⁺离子浓度较高时, 掺入的Sn⁴⁺离子在TiO₂表面生成金红石SnO₂, 形成TiO₂和SnO₂复合结构(TiO₂/SnO₂), SnO₂的导带位于TiO₂导带下0.33 eV处. 利用瞬态光电压谱和荧光光谱研究了TiO₂-Snx%催化剂光生载流子的分离和复合的动力学过程, 结果表明, Sn⁴⁺离子掺杂能级和表面SnO₂能带存在促进光生载流子的分离, 有效地抑制了光生电子与空穴的复合; 然而, Sn⁴⁺离子掺杂能级能更有效地增加光生电子的分离寿命, 提高了光生载流子的分离效率, 从而揭示了TiO₂-Snx%催化剂的光催化机理.

关键词: Sn⁴⁺离子掺杂TiO₂, Sn⁴⁺离子浓度, 瞬态光电压, 表面光电压谱, 光生电子的寿命

Abstract:

Pure TiO₂ and Sn⁴⁺ doped TiO₂ (TiO₂-Snx%) photocatalysts were prepared by a sol-gel method, where x% represents the nominal molar fraction of Sn⁴⁺ ions in the Zr⁴⁺ structure. The crystal structure and energy band structure of the resultant catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and surface photovoltage spectroscopy (SPS).The results show that for a low content of Sn⁴⁺ ions, the Sn⁴⁺ ions are doped into the TiO₂ lattice and replace lattice Ti⁴⁺ ions in a substitute mode (Ti_1-xSn_xO₂). The energy levels of these Sn⁴⁺ ions are located 0.38 eV below the conduction band. Moreover, the rutile SnO₂ crystal structure evolves with increasing content of Sn⁴⁺ ions, i.e., a TiO₂/SnO₂ structure is formed. The conduction band of SnO₂ is located 0.33 eV lower than that of TiO₂. The separation and recombination mechanism of the photo-generated carriers was characterized by photoluminescence and transient photovoltage techniques. The results showed that the formation of the energy levels of Sn⁴⁺ ions and the conduction band of rutile SnO₂ can enhance the separation of the photogenerated carriers, and suppress the recombination of photo-generated carriers. However, the energy levels of Sn⁴⁺ can lead to a much longer life time and higher separation efficiency of the photo-generated carriers. For different content of Sn⁴⁺ in Sn⁴⁺ ion doped TiO₂(TiO₂-Snx%), the abovementioned aspects improve the photocatalytic activity.

Key words: Sn⁴⁺-doped TiO₂, Content of Sn⁴⁺ ions, Transient photovoltage, Surface photovoltage spectroscopy, Life time of photo-generated electrons

MSC2000:

O648

张鹏, 赵路松, 姚江宏, 曹亚安. 不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性[J]. 物理化学学报, 2013, 29(06): 1305-1312.

ZHANG Peng, ZHAO Lu Song, YAO Jiang Hong, CAO Ya An. Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions[J]. Acta Phys. -Chim. Sin., 2013, 29(06): 1305-1312.

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不同浓度Sn⁴⁺离子掺杂TiO₂的结构、性质和光催化活性

Structure, Characterization and Photocatalytic Properties of TiO₂ Doped with Different Content of Sn⁴⁺ Ions

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