Cu/CeO_2(110)界面特性的第一性原理研究

A first-principle study on the interfacial properties of Cu/CeO_2 (110)

Cu-CeO2体系因其特殊的催化能力而在固体氧化物燃料电池和水煤气转化反应等多个催化领域有重要应用.采用基于密度泛函理论的第一性原理方法,在原子和电子层面上系统地研究了单个Cu原子及Cu小团簇在CeO2(110)面上的吸附构型,价键特性和电子结构,结果表明:1)单个Cu原子的最稳定吸附位是两个表面O的桥位;2)Cu团簇的稳定吸附构型为扭曲的四面体结构;3)Cu原子及Cu团簇的吸附在CeO2(110)面的gap区域引入了间隙态,这些间隙态主要来自于Cu及其近邻的O和表层还原形成的Ce3+,间隙态的出现表明Cu的吸附增强了CeO2(110)表面的活性;4)吸附的单个Cu原子及Cu团簇分别被CeO2(110)面表层的Ce4+离子氧化形成了Cuδ+和Cuδ+4,并伴随着Ce3+离子的形成,这个反应可归结为Cux/Ce4+→Cuδ+x/Ce3+;5)Cu团簇的吸附比Cu单原子的吸附引入了更多的Ce3+离子,进而形成了更多的Cuδ+-Ce3+催化活性中心.结合已报道的Cu/CeO2(111)界面特性,更加全面地探明了Cu与CeO2(111)和(110)两个较稳定低指数表面的协同作用特性,较为系统地揭示了Cu增强CeO2催化特性的原因及Cu与CeO2协同作用的内在机理.

Cu-CeO2 systems are widely used in solid oxide fuel cells and water gas shift reaction because of its special catalytic ability. The interracial properties of the Cu/CeO2 （110） with the adsorption of Cu atom and Cu cluster are investigated in terms of first- principles based on density functional theory. It is found that： 1） the single Cu adatom prefers to be adsorbed on the oxygen bridge site; 2） the adsorbed tetrahedron structure of Cu4 cluster is the most stable cluster configuration on CeO2（110） surface; 3） the metal- introduced gap states in the gap area are mainly from the adsorbed Cu （cluster）, its neighboring oxygen and the reduced cerium ion（s）, indicating that the activity of CeO2（110） surface is improved by copper adsorption; 4） the adsorbed Cu adatom and Cu4 cluster are oxidized to Cuδ＋ and Cu4δ＋ by their neighboring Ce ion（s） with the formation of Ce3＋ ion（s）, the reaction could be summarized as Cux/Ce4＋→Cuxδ＋/Ce3＋; 5） the adsorption of small clusters introduces more Ce3＋ ions than a single Cu atom does, indicating that more Cuδ＋-Ce3＋ catalytic active centers are formed. The current study on Cu/CeO2（110） together with our previous results on Cu/CeO2（111） presents a good understanding of the synergies between Cu and ceria, and reveals the improvement of the activity of ceria by Cu adsorption.