Photochemical Properties, Composition, and Structure in Molecular Beam Epitaxy Grown Fe "Doped" and (Fe,N) Codoped Rutile TiO2(110)

被引:28
作者
Mangham, Andrew N. [1 ]
Govind, Niranjan [1 ]
Bowden, Mark E. [1 ]
Shutthanandan, V. [1 ]
Joly, Alan G. [1 ]
Henderson, Michael A. [1 ]
Chambers, Scott A. [1 ]
机构
[1] Pacific NW Natl Lab, Fundamental & Computat Sci Directorate, Richland, WA 99352 USA
关键词
PHOTOINDUCED REDOX REACTION; QUANTUM-SIZED TIO2; METAL-ION DOPANTS; ELECTRONIC-STRUCTURE; TITANIUM-DIOXIDE; ULTRASOFT PSEUDOPOTENTIALS; PHOTOCATALYTIC ACTIVITY; TRIMETHYL ACETATE; N INCORPORATION; SURFACE;
D O I
10.1021/jp203061n
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have investigated the surface photochemical properties of Fe "doped" and (Fe,N) codoped homoepitaxial rutile TiO2(110) films grown by plasma-assisted molecular beam epitaxy. Fe does not incorporate as an electronic dopant in the rutile lattice but rather segregates to the film surface. However, codeposition of Fe with N enhances the solubility of Fe, and DFT calculations suggest that codopant complex formation is the driving force behind the enhanced solubility. The codoped films, in which a few atomic percent of Ti (O) are replaced with Fe (N), exhibit significant disorder compared to undoped films grown under the same conditions, presumably due to dopant-induced strain. Codoping redshifts the rutile bandgap into the visible. However, the film surfaces are photochemically inert with respect to hole-mediated decomposition of adsorbed trimethyl acetate. The absence of photochemical activity may result from dopant-induced trap and/or recombination sites within the film. This study indicates that enhanced visible light absorptivity in TiO2 does not necessarily result in visible light initiated surface photochemistry.
引用
收藏
页码:15416 / 15424
页数:9
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