苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究

引用本文: 王晨, 魏子章, 吕永康, 邢斌, 王贵昌. 苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201302043 shu

Citation: WANG Chen, WEI Zi-Zhang, LÜ Yong-Kang, XING Bin, WANG Gui-Chang. Theoretical Investigation of Structure-Sensitivity of Styrene Epoxidation on Ag(111) and Ag(110) Surfaces[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201302043 shu

苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究

王晨 ^1, ,
魏子章 ^2, ,
吕永康 ^1, ,
邢斌 ^3, ,
王贵昌 ^3,

基金项目:
国家自然科学基金(21078252)资助项目 (21078252)

摘要:

采用密度泛函理论(DFT)对苯乙烯在Ag(110)表面和Ag(111)表面的环氧化反应进行了计算研究. 经计算, 在Ag(110)表面预吸附氧原子更易吸附在3 重穴位(3h), 吸附能为-3.59 eV; 在Ag(111)表面预吸附氧原子的最稳定吸附位是fcc 位, 吸附能为-3.69 eV. 苯乙烯的环氧化反应过程首先经过一个金属中间体, 然后再进一步反应变为产物, 其中经过直链中间体较支链中间体更加有利. Ag(110)面的反应活化能一般大于Ag(111)面的, 并且微观动力学模拟结果表明, Ag(111)表面生成环氧苯乙烷的选择性要明显高于Ag(110)表面(0.38 与 0.003), 原因是Ag(111)面环氧化反应活化能小于苯乙醛及燃烧中间体的活化能, 而在Ag(110)上正相反.

关键词:

English

Theoretical Investigation of Structure-Sensitivity of Styrene Epoxidation on Ag(111) and Ag(110) Surfaces

1.
1 Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
2 Tianjin Enviromental Engineering Assessment Center, Tianjin 300191, P. R. China;
3 Department of Chemistry and the Tianjin Key Laboratory of Metal and Molecule-based Material Chemistry, Nankai University, Tianjin 300071, P. R. China
Received Date: 07 November 2012
Available Online: 25 March 2013
Fund Project:
国家自然科学基金(21078252)资助项目

Abstract:

The selective oxidation of styrene on oxygen-covered Ag(110) and Ag(111) surfaces is studied by density functional theory (DFT) calculations with the periodic slab model. On the Ag(110) surface, a pre-adsorbed oxygen atom prefers the 3-fold hollow site (3h) with an adsorption energy of -3.59 eV. On the Ag(111) surface, the most stable adsorption site for a pre-adsorbed oxygen atom is the fcc site, and the adsorption energy is -3.69 eV. The reaction process of the selective oxidation of styrene includes two steps: the formation of surface intermediates (branched oxametallacycle and linear oxametallacycle) and the subsequent formation of different products. The calculated results show that the formation of styrene oxide via the linear oxametallacycle (i.e., the pre-adsorbed atomic oxygen bound to the methylene group in styrene) is the favorable reaction mechanism on both Ag(110) and Ag(111) surfaces. The reaction barriers for the different reaction steps of styrene epoxidation on the Ag(110) surface are generally higher than those on the Ag(111) surface. Moreover, the micro-kinetic simulation results indicate that the relative selectivity towards the formation of styrene oxide on the Ag(111) surface is much higher than that on the Ag(110) surface (0.38 vs 0.003) because the energy barrier for the styrene epoxidation is smaller than that for the formation of phenyl acetaldehyde and its combustion intermediate on Ag(111) surface. The reverse trends occurred on the Ag(110) surface.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究

English

Theoretical Investigation of Structure-Sensitivity of Styrene Epoxidation on Ag(111) and Ag(110) Surfaces

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究

English

Theoretical Investigation of Structure-Sensitivity of Styrene Epoxidation on Ag(111) and Ag(110) Surfaces

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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