Hurum Deanna C, Gray Kimberly A, Rajh Tijana, Thurnauer Marion C
Institute for Environmental Catalysis and Department of Civil and Environmental Engineering, Northwestern University, Evanston, Illinois 60208, USA.
J Phys Chem B. 2005 Jan 20;109(2):977-80. doi: 10.1021/jp045395d.
Charge migration between electron trapping sites within the mixed-phase titania photocatalyst Degussa P25 has been studied. In addition to previously described lattice electron trapping sites on both anatase and rutile phases, surface electron trapping sites and an anatase-rutile interface trapping site specific to Degussa P25 are identified. The relationship between these sites and recombination with surface hole trapping sites is also determined. It is experimentally shown that upon band-gap illumination holes appear at the surface and preferentially recombine with electrons in surface trapping sites. These findings indicate that in mixed-phase TiO2, such as Degussa P25, photogenerated holes are trapped exclusively on the particle surface, while photogenerated electrons are trapped within the nanoparticle lattice. Recombination reactions are dominated by surface reactions that follow charge migration. These findings indicate that, in mixed-phase TiO(2), such as Degussa P25, a random flight mechanism of recombination predominates. Such knowledge simplifies the mechanistic mathematical models used for process design and points the way for improving future oxidative titania catalysts.
已对混合相二氧化钛光催化剂德固赛P25内电子俘获位点之间的电荷迁移进行了研究。除了之前描述的锐钛矿相和金红石相上的晶格电子俘获位点外,还确定了表面电子俘获位点以及德固赛P25特有的锐钛矿 - 金红石界面俘获位点。还确定了这些位点与表面空穴俘获位点复合之间的关系。实验表明,在带隙光照下,空穴出现在表面并优先与表面俘获位点中的电子复合。这些发现表明,在混合相TiO₂(如德固赛P25)中,光生空穴仅被俘获在颗粒表面,而光生电子被俘获在纳米颗粒晶格内。复合反应主要由电荷迁移后的表面反应主导。这些发现表明,在混合相TiO₂(如德固赛P25)中,复合的随机飞行机制占主导。这些知识简化了用于工艺设计的机理数学模型,并为改进未来的氧化钛催化剂指明了方向。