物理化学学报 >> 2016, Vol. 32 >> Issue (5): 1175-1182.doi: 10.3866/PKU.WHXB201602221

研究论文 上一篇    下一篇

铂钌团簇及电荷对甲醇活性的理论研究

赵俊凤,孙小丽,黄旭日,李吉来*()   

  • 收稿日期:2015-10-06 发布日期:2016-05-07
  • 通讯作者: 李吉来 E-mail:jilai@jlu.edu.cn
  • 基金资助:
    国家重点基础研究发展规划项目(973)(2012CB932800);国家自然科学基金(21103064);国家自然科学基金(21473070)

A Theoretical Study on the Reactivity and Charge Effect of PtRu Clusters toward Methanol Activation

Jun-Feng ZHAO,Xiao-Li SUN,Xu-Ri HUANG,Ji-Lai LI*()   

  • Received:2015-10-06 Published:2016-05-07
  • Contact: Ji-Lai LI E-mail:jilai@jlu.edu.cn
  • Supported by:
    the National Key Basic Research Program of China (973)(2012CB932800);National Natural Science Foundation of China(21103064);National Natural Science Foundation of China(21473070)

摘要:

采用密度泛函理论(DFT)对钌掺杂的铂团簇阳离子([PtnRum]+, m + n = 3, n ≥ 1)活化甲醇C―H和O―H键反应进行了理论研究;探讨了电荷对[PtnRum]团簇反应活性的影响。电荷分析表明:(1) [Pt3]+团簇中正电荷在三个Pt原子上均匀分布;掺杂Ru原子后,正电荷主要分布在Ru原子上; (2)首先活化C―H键时[PtnRum]+的反应活性比[PtnRum]明显提高;首先活化O―H键时只有[Pt3]+比[Pt3]团簇的反应活性有明显提高。本研究可为金属团簇调控的C―H键和O―H键的活化提供更深入的理解。

关键词: 密度泛函理论, 甲醇, 键活化, 电荷, 反应活性

Abstract:

Density functional theory (DFT) calculations were performed to gain mechanistic insight into the methanol C―H and O―H bond activations mediated by ruthenium-doped platinum cationic clusters [PtnRum]+ (m + n = 3, n ≥ 1). The charge effect on the reactivity has been elucidated. Calculations show that positive charge is evenly distributed on the three Pt atoms of the [Pt3]+ cluster, while in the Ru-doped clusters, positive charge is mainly distributed on the Ru atom(s). The reactivity of [PtnRum]+ is significantly greater than neutral [PtnRum] during the initial C―H bond cleavage, while only [Pt3]+ exhibits greater reactivity than [Pt3] in the course of O―H bond cleavage. This study may aid in deeper understanding of C―H/O―H bond activations mediated by metal clusters.

Key words: Density functional theory, Methanol, Bond activation, Charge, Reactivity

MSC2000: 

  • O641