Unique Electronic Structure Induced High Photoreactivity of Sulfur-Doped Graphitic C3N4

被引:1909
作者
Liu, Gang [1 ]
Niu, Ping [1 ]
Sun, Chenghua [2 ,3 ]
Smith, Sean C. [3 ]
Chen, Zhigang [2 ]
Lu, Gao Qing [2 ]
Cheng, Hui-Ming [1 ]
机构
[1] Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China
[2] Univ Queensland, ARC Ctr Excellence Funct Nanomat, Brisbane, Qld 4072, Australia
[3] Univ Queensland, Australia Inst Bioengn & Nanotechnol, Ctr Computat Mol Sci, Brisbane, Qld 4072, Australia
基金
中国博士后科学基金;
关键词
VISIBLE-LIGHT IRRADIATION; METAL-FREE CATALYSTS; CARBON NITRIDE; HYDROGEN-PRODUCTION; TITANIUM-DIOXIDE; PHOTOCATALYTIC ACTIVITY; WATER; SEMICONDUCTOR; TIO2; EVOLUTION;
D O I
10.1021/ja103798k
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Electronic structure intrinsically controls the light absorbance, redox potential, charge-carrier mobility, and consequently, photoreactivity of semiconductor photocatalysts. The conventional approach of modifying the electronic structure of a semiconductor photocatalyst for a wider absorption range by anion doping operates at the cost of reduced redox potentials and/or charge-carrier mobility, so that its photoreactivity is usually limited and some important reactions may not occur at all. Here, we report sulfur-doped graphitic C3N4 (C3N4-xSx) with a unique electronic structure that displays an increased valence bandwidth in combination with an elevated conduction band minimum and a slightly reduced absorbance. The C3N4-xSx shows a photoreactivity of H-2 evolution 7.2 and 8.0 times higher than C3N4 under lambda > 300 and 420 nm, respectively. More strikingly, the complete oxidation process of phenol under lambda > 400 nm can occur for sulfur-doped C3N4, which is impossible for C3N4 even under lambda > 300 nm. The homogeneous substitution of sulfur for lattice nitrogen and a concomitant quantum confinement effect are identified as the cause of this unique electronic structure and, consequently, the excellent photoreactivity of C3N4-xSx. The results acquired may shed light on general doping strategies for designing potentially efficient photocatalysts.
引用
收藏
页码:11642 / 11648
页数:7
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