Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (12): 2224-2232.doi: 10.3866/PKU.WHXB201410101

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Configuration and Electronic Structure of W3O9 Clusters Supported on Li- and Al-Doped MgO(001) Surfaces

LUO Yun-Qing1, QIU Mei1, YANG Wei1, ZHU Jia2, LI Yi1, HUANG Xin1, ZHANG Yong-Fan1   

  1. 1. College of Chemistry, Fuzhou University, Fuzhou 350116, P. R. China;
    2. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China
  • Received:2014-07-28 Revised:2014-10-10 Published:2014-11-27
  • Contact: ZHANG Yong-Fan E-mail:zhangyf@fzu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21373048, 21371034, 21403094), Natural Science Foundation of Fujian Province for Distinguished Young Investigator Grant, China (2013J06004), and Fund of Jiangxi Province Office of Education, China (GJJ14261).

Abstract:

The configuration, stability, and electronic structure of W3O9 clusters deposited on Li- and Al-doped MgO(001) surfaces were investigated using first- principles molecular dynamic simulations combined with quantum mechanical calculations. The results indicated that when the doping was in the top layer of the MgO (001) surface, the type of dopant had a great influence on the configuration of theW3O9 clusters. In the presence of electron-deficient Li doping, the cyclic conformation of the gas-phase W3O9 clusters was not stable, and it changed to a chain-like structure. While the introduction of the Al dopant made the surface electron-rich, the W3O9 clusters preferred parallel and vertical arrangements, respectively; the stabilities of the two configurations were similar, except that in the former case the one terminal oxygen of the clusters became a capped oxygen via bonding with three W atoms. When the doping was present in the sublayer, the W3O9 clusters still showed a cyclic conformation, and favored a vertical deposition model. In comparison with the Li-doping of the MgO(001) surface, the Al-doping significantly enhanced the interactions between theW3O9 and the MgO(001) surface, and more electrons were transferred from the substrate to certain W atoms, which would have significant effects on the catalytic performance of the W3O9 clusters.

Key words: Tungsten oxide cluster, Doping, MgO surface, Density functional theory, Electronic structure

MSC2000: 

  • O641