物理化学学报 >> 2016, Vol. 32 >> Issue (4): 950-960.doi: 10.3866/PKU.WHXB201601191

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碱性介质中CO对甲醇在PtAu(111)和Pt(111)表面氧化生成甲酸的影响的第一性原理研究

刘建红1,吕存琴1,2,晋春1,*(),王贵昌3,*()   

  1. 1 山西大同大学化学与环境工程学院, 山西大同 037009
    2 先进能源材料化学教育部重点实验室(南开大学), 天津 300071
    3 南开大学化学学院, 天津市金属与分子基材料化学重点实验室(南开大学), 天津 300071
  • 收稿日期:2015-09-28 发布日期:2016-04-07
  • 通讯作者: 晋春,王贵昌 E-mail:jinchun0828@126.com;wangguichang@nankai.edu.cn
  • 基金资助:
    国家自然科学基金(21503122, 21346002);山西省青年科技研究基金(2014021016-2);山西省科技攻关项目(2015031017);先进能源材料化学教育部重点实验室开放基金

First-Principles Study of Effect of CO to Oxidize Methanol to Formic Acid in Alkaline Media on PtAu(111) and Pt(111) Surfaces

Jian-Hong LIU1,Cun-Qin Lü1,2,Chun JIN1,*(),Gui-Chang WANG3,*()   

  1. 1 College of Chemistry and Enviromental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province, P. R. China
    2 Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, 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:2015-09-28 Published:2016-04-07
  • Contact: Chun JIN,Gui-Chang WANG E-mail:jinchun0828@126.com;wangguichang@nankai.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21503122, 21346002);Natural Science Foundation of Shanxi forYouths, China(2014021016-2);Scientific and Technological Programs in Shanxi Province, China(2015031017);Foundation of Key Laboratoryof Advanced Energy Materials Chemistry (Ministry of Education), China

摘要:

采用密度泛函理论计算研究了碱性介质中甲醇在清洁的PtAu(111)和Pt(111)表面、及有CO存在的PtAu(111)和Pt(111)表面的氧化。计算结果表明,在碱性介质中,预吸附的CO促进了甲醇在PtAu(111)和Pt(111)表面氧化的每一步反应,这与其在Au(111)表面的作用相似。究其原因,是由于CO的吸附增强了OH的稳定性和碱性,从而增强了OH夺取氢原子的能力。

关键词: 甲醇氧化, M(111) (M = PtAu, Pt), 碱性介质, CO促进作用, 密度泛函理论计算

Abstract:

Density functional theory calculations have been performed to investigate methanol oxidation to formic acid on PtAu(111) and Pt(111) surfaces with and without CO in alkaline media. The calculated results show that the pre-adsorbed CO species promotes almost every step involved in the oxidation of methanol on PtAu(111) and Pt(111) surfaces, which is similar to that observed on a Au(111) surface. These findings may be attributed to the relatively high stability and strong basicity of the OH species induced by the adsorption of CO, and the enhanced ability to strip the H atoms.

Key words: Methanol oxidation, M(111) (M = PtAu, Pt), Alkaline medium, CO promotion effect, Density functional theory calculation

MSC2000: 

  • O641