Li和Al掺杂的M (001)表面负载W<sub>3</sub>O<sub>9</sub>团簇的构型与电子结构

引用本文: 罗云清, 邱美, 杨伟, 朱佳, 李奕, 黄昕, 章永凡. Li和Al掺杂的M (001)表面负载W₃O₉团簇的构型与电子结构[J]. 物理化学学报, 2014, 30(12): 2224-2232. doi: 10.3866/PKU.WHXB201410101 shu

Citation: LUO Yun-Qing, QIU Mei, YANG Wei, ZHU Jia, LI Yi, HUANG Xin, ZHANG Yong-Fan. Configuration and Electronic Structure of W₃O₉ Clusters Supported on Li- and Al-Doped M (001) Surfaces[J]. Acta Physico-Chimica Sinica, 2014, 30(12): 2224-2232. doi: 10.3866/PKU.WHXB201410101 shu

Li和Al掺杂的M (001)表面负载W₃O₉团簇的构型与电子结构

罗云清 ^1, ,
邱美 ^1, ,
杨伟 ^1, ,
朱佳 ^2, ,
李奕 ^1, ,
黄昕 ^1, ,
章永凡 ^1,

基金项目:
国家自然科学基金(21373048, 21371034, 21403094) (21373048, 21371034, 21403094)

福建省杰出青年科学基金(2013J06004) (2013J06004)

江西省教育厅(GJJ14261)资助项目 (GJJ14261)

摘要:

采用基于第一性原理的分子动力学和量子力学相结合的方法, 对W₃O₉团簇在经Li 和Al 原子掺杂的M (001)表面的负载构型、稳定性以及体系的电子结构进行了系统研究. 结果表明, 当掺杂发生在表层时, 杂质原子的类型对W₃O₉团簇的负载构型有显著影响. 对于缺电子的Li 掺杂, 负载后W₃O₉团簇环状构型并不稳定, 转化为链状结构; 而Al 原子的掺杂则使得M (001)表面电子富余, 此时W₃O₉团簇存在平躺和垂直两种吸附方式, 二者能量稳定性相近, 其中前者存在同时与三个W原子成键的帽氧结构. 当掺杂发生在次表层时, 两种掺杂体系W₃O₉的负载构型相似, 团簇仍保持环状结构并倾向于采用垂直方式沉积在表面上. 与Li 掺杂体系相比, 富电子的Al 掺杂可显著增强W₃O₉与M (001)表面之间的结合能力, 负载后有较多电子从表面转移到团簇中特定的W原子上, 这将对W₃O₉团簇的催化性能产生显著影响.

关键词:

English

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

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 Date: 28 July 2014
Available Online: 27 November 2014
Fund Project:
国家自然科学基金(21373048, 21371034, 21403094)

福建省杰出青年科学基金(2013J06004)

江西省教育厅(GJJ14261)资助项目

Abstract:

The configuration, stability, and electronic structure of W₃O₉ clusters deposited on Li- and Al-doped M (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 M (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 M (001) surface, the Al-doping significantly enhanced the interactions between theW₃O₉ and the M (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:

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沈阳化工大学材料科学与工程学院沈阳 110142

Li和Al掺杂的M (001)表面负载W₃O₉团簇的构型与电子结构

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