Stepwise Photocatalytic Dissociation of Methanol and Water on TiO2(110)

被引:256
作者
Guo, Qing [1 ]
Xu, Chenbiao [1 ,3 ]
Ren, Zefeng [1 ]
Yang, Wenshao [1 ]
Ma, Zhibo [1 ]
Dai, Dongxu [1 ]
Fan, Hongjun [1 ]
Minton, Timothy K. [2 ]
Yang, Xueming [1 ]
机构
[1] Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
[2] Montana State Univ, Dept Chem & Biochem, Bozeman, MT 59717 USA
[3] Dalian Univ Technol, Sch Phys & Optoelect Engn, Dalian 59717, Liaoning, Peoples R China
基金
中国国家自然科学基金; 美国国家科学基金会;
关键词
MINIMUM ENERGY PATHS; ELASTIC BAND METHOD; AB-INITIO; TIO2; 110; ELECTRON-TRANSFER; TITANIUM-DIOXIDE; SURFACE SCIENCE; SADDLE-POINTS; ADSORPTION; PRINCIPLES;
D O I
10.1021/ja304049x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have investigated the photocatalysis of partially deuterated methanol (CD3OH) and H2O on TiO2(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD2O on Ti-sc sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD3OH have been clearly detected, while no evidence of H2O photocatalysis was found. The experimental results show that dissociation of CD3OH on TiO2(110) occurs in a stepwise manner in which the O-H dissociation proceeds first and is then followed by C-D dissociation. Theoretical calculations indicate that the high reverse barrier to C-D recombination and the facile desorption of CD2O make photocatalytic methanol dissociation on TiO2(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O-H recombination after H2O photocatalytic dissociation on TiO2(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.
引用
收藏
页码:13366 / 13373
页数:8
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