CO和CH3O在Cu2O(111)表面吸附特性及共吸附的理论研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1246.

CO和CH₃O在Cu₂O(111)表面吸附特性及共吸附的理论研究

章日光, 郑华艳, 王宝俊, 李忠

太原理工大学煤科学与技术教育部和山西省重点实验室, 太原 030024

收稿日期:2009-09-27 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 李忠, 男, 博士, 教授, 博士生导师, 主要从事一碳化学研究. E-mail: lizhong@tyut.edu.cn
基金资助:
国家自然科学基金(批准号: 20906066, 20976113, 20976115)和国家“九七三”计划项目(批准号: 2005CB221204)资助.

Theoretical Study on the Properties of CO and CH₃O Adsorption on Cu₂O(111) Surface and Co-adsorption

ZHANG Ri-Guang, ZHENG Hua-Yan, WANG Bao-Jun, LI Zhong*

Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China

Received:2009-09-27 Online:2010-06-10 Published:2010-06-10
Contact: LI Zhong. E-mail: lizhong@tyut.edu.cn
Supported by:
国家自然科学基金(批准号: 20906066, 20976113, 20976115)和国家“九七三”计划项目(批准号: 2005CB221204)资助.

摘要/Abstract

摘要：

基于密度泛函理论, 采用广义梯度近似方法结合周期平板模型, 对Cu₂O(111)非极性表面上CO和CH₃O的吸附和共吸附进行了系统的研究. 计算了CO以4种吸附模式和CH₃O以O端在Cu₂O(111)表面上的吸附, 通过对不同吸附位置的吸附能、几何构型参数和Mulliken电荷的计算和比较发现, Cu₂O(111)表面上配位未饱和铜离子(Cu_CUS)为CO的活性吸附位; 配位饱和铜离子(Cu_CSA)为CH₃O的活性吸附位. CO和CH₃O吸附于Cu₂O(111)表面后, 表面弛豫现象明显改善. CO和CH₃O与Cu₂O(111)表面能够形成共吸附体系, CO和CH₃O之间的相互作用力达到75.89 kJ/mol, 为典型的化学作用, 有助于促进CO和CH₃O反应形成表面物种CH₃OCO, 计算结果与实验事实一致.

关键词: CO; CH3O; Cu2O(111)表面; 吸附; 密度泛函理论

Abstract:

Based on density functional theory in the generalized gradient approximation, together with periodic slab model, CO and CH₃O adsorption and co-adsorption on Cu₂O(111) non-polar surface were systematically investigated. Four molecular orientations of CO and O-down orientation of CH₃O over different adsorption sites, Cu_CUS, Cu_CSA, O_SUF and O_SUB of the Cu₂O(111) surface were considered. The adsorption energy, geometrical parameter and Mulliken charge indicate that Cu_CUS is the active site for CO adsorption, Cu_CSA is the active site for CH₃O adsorption. CO and CH₃O adsorption mode improves the relaxation of Cu₂O(111) surface. In co-adsorption system, the interaction between CO and CH₃O is 75.89 kJ/mol, which help to product CH₃OCO, the calculated results are in agreement with experimental facts.

Key words: Carbon monoxide; Methoxide; Cu2O(111) surface; Adsorption; Density functional theory

TrendMD:

章日光, 郑华艳, 王宝俊, 李忠. CO和CH₃O在Cu₂O(111)表面吸附特性及共吸附的理论研究. 高等学校化学学报, 2010, 31(6): 1246.

ZHANG Ri-Guang, ZHENG Hua-Yan, WANG Bao-Jun, LI Zhong*. Theoretical Study on the Properties of CO and CH₃O Adsorption on Cu₂O(111) Surface and Co-adsorption. Chem. J. Chinese Universities, 2010, 31(6): 1246.

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CO和CH₃O在Cu₂O(111)表面吸附特性及共吸附的理论研究

Theoretical Study on the Properties of CO and CH₃O Adsorption on Cu₂O(111) Surface and Co-adsorption

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