Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (07): 1461-1466.doi: 10.3866/PKU.WHXB201304081

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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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