金属簇X (X=Pt-Au, Au-Au)负载在(3×2) TiO2(110)完整表面上的覆盖度效应

doi:10.3866/PKU.WHXB201205214

物理化学学报 >> 2012, Vol. 28 >> Issue (08): 1861-1868.doi: 10.3866/PKU.WHXB201205214

金属簇X (X=Pt-Au, Au-Au)负载在(3×2) TiO₂(110)完整表面上的覆盖度效应

赵伟娜¹, 林华香², 李奕¹, 章永凡¹, 黄昕¹, 陈文凯^1,2

1. 福州大学化学化工学院, 福州 350116;
2. 福州大学省部共建光催化国家重点实验室培育基地, 福州 350002

收稿日期:2012-03-20 修回日期:2012-05-21 发布日期:2012-07-10
通讯作者: 陈文凯 E-mail:qc2008@fzu.edu.cn
基金资助:
国家自然科学基金(90922022)和华中科技大学煤燃烧国家重点实验室开放基金(FSKLCC1110)资助项目

Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface

ZHAO Wei-Na¹, LIN Hua-Xiang², LI Yi¹, ZHANG Yong-Fan¹, HUANG Xin¹, CHEN Wen-Kai^1,2

1. College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350116, P. R. China;
2. Fujian Provincial Key Laboratory of Photocatalysis-State Key Laboratory Breeding Base, Fuzhou University, Fuzhou 350002, Fujian, P. R. China

Received:2012-03-20 Revised:2012-05-21 Published:2012-07-10
Contact: CHEN Wen-Kai E-mail:qc2008@fzu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (90922022) and Foundation of State Key Laboratory of Coal Combustion of Huazhong University of Science and Technology, China (FSKLCC1110).

摘要/Abstract

摘要：

采用自旋极化密度泛函和广义梯度近似的方法并结合周期平板模型, 探讨了不同覆盖度(θ)下双金属簇X (X=Pt-Au, Au-Au)在(3×2)TiO₂(110)完整表面上的吸附行为. 另外, 在本文给出的所有覆盖度模式下(θ= 1/6-1 ML), 我们仅研究其基态构型. 计算结果表明: 当θ<1/2 ML时, 金属簇X在TiO₂(110)表面上吸附能随覆盖度的增加而增加; 当θ>1/2 ML时, 除了饱和覆盖度下, 吸附能随覆盖度的增加而减小; 当θ=1/2 ML时, 吸附能最大. 即使Pt-Au/TiO₂体系的吸附能比Au-Au/TiO₂体系的小, 但相对于Au-Au 簇, Pt-Au 簇更容易在TiO₂(110)表面上形成双金属单分子层. 在半覆盖和全覆盖下, X簇的峰与TiO₂的峰在-3.0 eV到费米能级之间产生明显重叠, 表明簇与底物之间存在化学作用. 且当覆盖度小时, X-TiO₂相互作用是成簇的主要因素; 随着覆盖度的增大, X-X原子间相互作用就逐渐变成了成簇的主要动力.

关键词: 密度泛函理论, TiO₂ (110)表面, 双金属簇

Abstract:

Based on spin-polarized density functional theory and generalized gradient approximation (DFT-GGA) calculations, the coverage-dependent adsorption of X bimetallic clusters (X=Pt-Au, Au-Au) on the (3 × 2) TiO₂(110) surface has been investigated utilizing periodic supercell models in the absence of oxygen vacancy sites. Only the ground-state structures corresponding to the given coverage patterns (θ= 1/6-1 ML) for X clusters are discussed in this work. The unambiguous results reveal that the adsorption energies increase with coverage up to 1/2 ML and then decrease except for when saturated coverage is reached. According to the interaction with X clusters, it is more feasible at all coverage levels to create a monolayer film of Pt-Au bimetallic clusters on the TiO₂(110) surface than it is to create a monolayer of Au- Au clusters, even though the adsorption energy of the Pt-Au/TiO₂ adsorption system is smaller in comparison with that of the Au-Au/TiO₂ system. Importantly, especially for the half and saturated coverages, there is a broadening of X peaks overlapping with the TiO₂ state ranging from -3.0 eV to the Fermi level, suggesting a strong interaction between the surface and bimetallic cluster. Also of particular interest is the adsorptive mechanism where the X-TiO₂ interaction is the main driving force at the initial stage of the adsorption process, whereas the X-X interaction controls the process as the coverage increases.

Key words: Density functional theory, TiO₂ (110) surface, Bimetallic cluster

赵伟娜, 林华香, 李奕, 章永凡, 黄昕, 陈文凯. 金属簇X (X=Pt-Au, Au-Au)负载在(3×2) TiO₂(110)完整表面上的覆盖度效应[J]. 物理化学学报, 2012, 28(08): 1861-1868.

ZHAO Wei-Na, LIN Hua-Xiang, LI Yi, ZHANG Yong-Fan, HUANG Xin, CHEN Wen-Kai. Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface[J]. Acta Phys. -Chim. Sin., 2012, 28(08): 1861-1868.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201205214

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I08/1861

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金属簇X (X=Pt-Au, Au-Au)负载在(3×2) TiO₂(110)完整表面上的覆盖度效应

Coverage-Dependent Adsorption of X Clusters (X=Pt-Au, Au-Au) on the Defect-Free (3×2) TiO₂(110) Surface

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