物理化学学报 >> 2016, Vol. 32 >> Issue (7): 1674-1680.doi: 10.3866/PKU.WHXB2016032806

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Al2O3/Au(111)反相催化剂在CO氧化反应中界面作用的理论研究

顾勇冰1,3,蔡秋霞1,陈先朗1,庄镇展1,周虎1,庄桂林1,钟兴1,梅东海2,王建国1,*()   

  1. 1 浙江工业大学化学工程学院,杭州310032
    2 美国西北太平洋国家实验室催化研究所,里奇兰99352,华盛顿州,美国
    3 丽水学院化学化工系,浙江丽水323000
  • 收稿日期:2016-01-23 发布日期:2016-07-08
  • 通讯作者: 王建国 E-mail:jgw@zjut.edu.cn
  • 基金资助:
    国家重点基础研究发展规划项目(973)(2013CB733501);国家自然科学基金项目(21176221);国家自然科学基金项目(21136001);国家自然科学基金项目(21101137);国家自然科学基金项目(21306169);国家自然科学基金项目(91334013)

Theoretical Insights into Role of Interface for CO Oxidation on Inverse Al2O3/Au(111) Catalysts

Yong-Bing GU1,3,Qiu-Xia CAI1,Xian-Lang CHEN1,Zhen-Zhan ZHUANG1,Hu ZHOU1,Gui-Lin ZHUANG1,Xing ZHONG1,Dong-Hai MEI2,Jian-Guo WANG1,*()   

  1. 1 College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China
    2 Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland 99352, Washington, USA
    3 Department of Chemistry and Chemical Engineering, Lishui University, Lishui 323000, Zhejiang Province, P. R. China
  • Received:2016-01-23 Published:2016-07-08
  • Contact: Jian-Guo WANG E-mail:jgw@zjut.edu.cn
  • Supported by:
    the National Key Basic Research Program of China (973)(2013CB733501);National Natural Science Foundation of China(21176221);National Natural Science Foundation of China(21136001);National Natural Science Foundation of China(21101137);National Natural Science Foundation of China(21306169);National Natural Science Foundation of China(91334013)

摘要:

氧化物负载的金催化剂具有温和条件下优异的CO催化氧化活性。实验与理论计算表明,金与氧化物两相界面在催化反应过程中具有重要地位。反相催化剂提供了全新的角度以探究界面的重要地位。本文以Au(111)表面负载Al2O3团簇为反相催化剂模型,基于密度泛函理论,对催化剂模型的构型、界面性质以及O2、CO的吸附与氧化进行了理论计算与研究。理论计算表明:电荷的迁移增强了Al2O3小团簇在Au(111)表面的附着,在催化剂金表面与氧化铝的两相界面位置,Au原子与Al原子的协同作用使得氧分子易于在界面位置吸附,并因此高度活化。对催化CO氧化反应路径,分别计算了缔合机理和解离机理不同路径,从活化能分析表明缔合机理比解离机理更可能发生。本文的工作揭示了反相催化剂催化CO氧化的活性本质,表明两相界面在金催化CO氧化中具有重要作用。

关键词: 反相催化剂, 金催化剂, CO氧化, 密度泛函理论, 界面位

Abstract:

Au catalysts supported on an oxide show excellent activity in CO oxidation under moderate conditions. Many experiments and theoretical calculations have shown the important role of the interface between Au and the oxide support during CO oxidation. Inverse catalysts provide an alternative way to probe the role of the interface. We used Al2O3/Au(111) as a model inverse catalyst in this study, and used density functional theory to investigate the properties of Al2O3/Au(111), the interface between Al2O3 and Au(111), the adsorption of O2, and CO oxidation over Al2O3/Au(111). Our theoretical calculations show that small Al2O3 clusters are strongly bound on the Au(111) surface as a result of charge transfer. The results for O2 adsorption on different sites indicate that the interfacial site is the most stable one because of simultaneous bonding of O2 with Au and Al atoms. The full catalytic cycles for CO oxidation by O2 by either an association or dissociation pathway were investigated. Oxidation in the association pathway is significantly easier than that in the dissociation one; the participation of CO makes dissociation of the adsorbed O2 easier. This study reveals not only the origin of inverse catalysts for CO oxidation but also the role of the interface in CO oxidation on Au catalysts.

Key words: Inverse catalyst, Au catalyst, CO oxidation, Density functional theory, Interfacial site

MSC2000: 

  • O641