物理化学学报 >> 2013, Vol. 29 >> Issue (07): 1461-1466.doi: 10.3866/PKU.WHXB201304081

理论与计算化学 上一篇    下一篇

均苯四甲酰亚胺桥联的聚酞菁亚铁的氧还原反应

孙晓然1,3, 李光跃3, 夏定国2, 张立美3, 李钒1   

  1. 1 北京工业大学化学与环境工程学院, 北京 100086;
    2 北京大学工学院, 北京 100871;
    3 河北联合大学化学工程学院, 唐山 063009
  • 收稿日期:2013-01-18 修回日期:2013-04-08 发布日期:2013-06-14
  • 通讯作者: 孙晓然 E-mail:xiaoranhb@yeah.net
  • 基金资助:

    国家自然科学基金(11247281); 北京市自然科学基金(2120001)和河北省优秀青年基金(Y2012010)资助项目

Oxygen-Reduction Reaction of Pyromellitimide-Bridged Polyphthalocyanine Fe(II)

SUN Xiao-Ran1,3, LI Guang-Yue3, XIA Ding-Guo2, ZHANG Li-Mei3, LI Fan1   

  1. 1 College of Chemical and Envioramental Engineering, Beijing Industry University, Beijing 100086, P. R. China;
    2 College of Engineering, Peking University, Beijing 100871, P. R. China;
    3 College of Chemical Engineering, Hebei United University, Tangshan 063009, Hebei Province, P. R. China
  • Received:2013-01-18 Revised:2013-04-08 Published:2013-06-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (11247281), Beijing Natural Science Foundation, China (2120001) and Excellent Youth Fund of Hebei Province Department of Education, China (Y2012010).

摘要:

用密度泛函方法研究了一种均苯四甲酰亚胺桥联的聚酞菁亚铁的氧还原反应. 设计了三个模型分子以研究此催化剂在不同聚合度时的氧还原催化反应性能. 使用BP86 泛函和SVP基组进行构型优化得到模型分子及其氧气复合物的电子和分子结构. 此催化剂中心的铁原子和氧气以双键结合并发生电荷转移时, 氧气被还原. 这证明此催化剂具有良好的催化氧还原能力. 通过前沿轨道分析以及模型分子氧气复合物稳定性分析证实, 具有较高聚合度和较强吸电子取代基的催化剂具有更好的氧还原活性. 催化剂的催化性能通过一个电催化循环来实现. 在此循环过程中, 氧气结合氢离子被还原为水, 因此此催化剂需要在酸性介质中使用.

关键词: 聚酞菁, 铁, 氧还原, 反应性, 密度泛函理论

Abstract:

The activity of a pyromellitimide-bridged polyphthalocyanine Fe(II) catalyst for O2 reduction is studied by density functional theory calculations. Three model molecules with different polymerization degrees are designed to investigate O2-reduction electrocatalytic reactivity. The molecular and electronic structures of the models and their O2-complexes are optimized with BP86 functional and SVP basis sets. The central Fe atom in the catalyst binds O2 by a double bond followed by a charge transfer to reduce O2. This study indicates that the catalyst has potential for O2-reduction electrocatalytic activity. The calculated frontier molecular orbitals and stabilities of the O2-complexes demonstrate that catalysts with a higher polymerization degree and stronger electron-withdrawing groups will have higher activities for O2 reduction. O2-reduction activity of the catalyst is achieved via an electrocatalytic cycle.

Key words: Polyphthalocyanine, Fe, Oxygen-reduction, Reactivity, Density functional theory

MSC2000: 

  • O646