物理化学学报 >> 2015, Vol. 31 >> Issue (5): 885-892.doi: 10.3866/PKU.WHXB201503181

理论与计算化学 上一篇    下一篇

正二十面体Au13和Pt13团簇上肉桂醛的吸附

肖雪春, 施炜, 倪哲明, 张连阳, 徐金芳   

  1. 浙江工业大学化学工程学院, 先进催化材料实验室, 杭州310014
  • 收稿日期:2015-02-05 修回日期:2015-03-17 发布日期:2015-05-08
  • 通讯作者: 倪哲明 E-mail:jchx@zjut.edu.cn

Adsorption of Cinnamaldehyde on Icosahedral Au13 and Pt13 Clusters

XIAO Xue-Chun, SHI Wei, NI Zhe-Ming, ZHANG Lian-Yang, XU Jin-Fang   

  1. Laboratory of Advanced Catalytic Materials, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. China
  • Received:2015-02-05 Revised:2015-03-17 Published:2015-05-08
  • Contact: NI Zhe-Ming E-mail:jchx@zjut.edu.cn

摘要:

运用广义梯度近似(GGA)密度泛函理论的Perdew-Burke-Ernzerh (PBE)方法, 研究了肉桂醛在正二十面体Au13和Pt13团簇上的吸附行为. 通过分析不同吸附模式的吸附能和几何构型发现: 同一金属团簇, 顺式肉桂醛的吸附能强于反式肉桂醛的吸附能. 对于Au13团簇, 肉桂醛的稳定吸附构型为C=C和C=O共吸附模型; 对于Pt13团簇, 肉桂醛的稳定吸附构型为C=O吸附. 比较二者发现, 肉桂醛在Pt13团簇的吸附能力强于Au13团簇.分析Au13和Pt13团簇上肉桂醛最稳定吸附构型的电子结构表明, 电子由肉桂醛原子的2s、2p轨道向金属表面转移, 同时金属部分电子反馈到肉桂醛的反键轨道, 最终肉桂醛稳定吸附于金属团簇. 此外, 肉桂醛在团簇模型上的吸附能大于其在平板模型上的吸附能.

关键词: 肉桂醛, 密度泛函理论, 吸附, Au13团簇, Pt13团簇

Abstract:

The adsorption behavior of cinnamaldehyde on icosahedral Au13 and Pt13 clusters was investigated by density functional theory with the Perdew-Burke-Ernzerh of generalized gradient approximation (GGA-PBE). When analyzing the adsorption energies and geometrical parameters of different adsorption models, the adsorption energy of cis-cinnamaldehyde was higher than that of trans-cinnamaldehyde for the same cluster. On the Au13 cluster, the most stable adsorption was the C=O and C=C double bond coadsorption model. While on the Pt13 cluster, the most stable adsorption was the C=O double bond adsorption model. Comparison between the Au13 and Pt13 clusters showed that the adsorption capacity of cinnamaldehyde on the Pt13 cluster was higher than on the Au13 cluster. Analyzing the electronic structures of the most stable adsorption configurations of cinnamaldehyde on the Au13 and Pt13 clusters showed that electrons transferred from 2s and 2p orbitals of cinnamaldehyde to the metal clusters. Electrons of metal clusters were also back-donated to the anti-bonding orbitals of the cinnamaldehyde molecule. This collaborative process eventually led to the stable adsorption of cinnamaldehyde on the Au13 and Pt13 clusters. In addition, adsorption of cinnamaldehyde on cluster models was more energetically favorable than on flat models.

Key words: Cinnamaldehyde, Density functional theory, Adsorption, Au13 cluster, Pt13 cluster

MSC2000: 

  • O641