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Photoinduced Decomposition of Formaldehyde on Rutile TiO2(100)-(1×1)
Xiao Chen,Fang-liang Li,Qing Guo*,Dong-xu Dai,Xue-ming Yang*
Author NameAffiliationE-mail
Xiao Chen State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China;University of Chinese Academy of Sciences, Beijing 100049, China  
Fang-liang Li University of Chinese Academy of Sciences, Beijing 100049, China;School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China  
Qing Guo* State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China guoqing@dicp.ac.cn 
Dong-xu Dai State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China  
Xue-ming Yang* State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China xmyang@dicp.ac.cn 
Abstract:
We have investigated the photoinduced decomposition of formaldehyde (CH2O) on a rutile TiO2(100)-(1×1) surface at 355 nm using temperature-programmed desorption. Products, formate (HCOO-), methyl radical (CH3·), ethylene (C2H4), and methanol (CH3OH) have been detected. The initial step in the decomposition of CH2O on the rutile TiO2(100)-(1×1) surface is the formation of a dioxymethylene intermediate in which the carbonyl O atom of CH2O is bound to a Ti atom at the five-fold-coordinated Ti4+ (Ti5c) site and its carbonyl C atom bound to a nearby bridge-bonded oxygen (Ob) atom, respectively. During 355 nm irradiation, the dioxymethylene intermediate can transfer an H atom to the Ob atom, thus forming HCOO- directly, which is considered as the main reaction channel. In addition, the dioxymethylene intermediate can also transfer methylene to the Ob row and break the C-O bond, thus leaving the original carbonyl O atom at the Ti5c site. After the transfer of methylene, several pathways to products are available. Thus, we have found that Ob atoms are intimately involved in the photoinduced decomposition of CH2O on the rutile TiO2(100)-(1×1) surface.
Key words:  Rutile TiO2(100)-(1× 1)  Formaldehyde  Temperature-programmed desorption  Photoinduced decomposition
FundProject:This work was supported by the National Natural Science Foundation of China (No.21673235 and No.21403224), and the Youth Innovation Promotion Association CAS, and the Key Research Program of the Chinese Academy of Sciences.
甲醛在金红石型TiO2(100)-(1×1)表面的光解离
陈晓,李方亮,郭庆*,戴东旭,杨学明*
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DOI:10.1063/1674-0068/31/cjcp1806137
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