上海交通大学学报(自然版) ›› 2017, Vol. 51 ›› Issue (12): 1422-1427.doi: 10.16183/j.cnki.jsjtu.2017.12.003

• 学报(中文) • 上一篇    下一篇

基于密度泛函理论的过渡金属酞菁配合物氧还原反应催化能力

周苏,姜缜,DE LILE J R   

  1. 同济大学 a. 汽车学院; b. 中德学院, 上海 201804
  • 出版日期:2017-11-30 发布日期:2017-11-30

Catalytic Capacity of Transition Metal Phthalocyanine Complexes Based on Density Functional Theory

ZHOU Su,JIANG Zhen,DE LILE J R   

  1. a. School of Automotive Studies; b. CDHK, Tongji University, Shanghai 201804, China
  • Online:2017-11-30 Published:2017-11-30

摘要: 通过分析钛酞菁(TiPc)、铁酞菁(FePc)、钴酞菁(CoPc)、铜酞菁(CuPc)和镍酞菁(NiPc)5种过渡金属酞菁配合物(TMPcs)的O2吸附能、OH吸附能、H2O2吸附能和H2O吸附能,发现TMPcs的氧还原能力与O2吸附能有一定关系,O2吸附能越大,其氧还原反应催化能力越强.基于密度泛函理论(DFT)和量子力学原理,计算了TiPc的相关吸附能,结果显示:在5种TMPcs中TiPc的O2吸附能力最强;TiPc的O2吸附能大于其OH吸附能;TiPc的O2吸附能远大于其H2O吸附能.在分析TMPcs反应机理的基础上,根据氧还原反应中吉布斯自由能的变化,比较TiPc、FePc、CoPc和Pt作为催化剂的4种情况,理论计算结果表明,TiPc作为催化剂的氧还原反应过程中没有明显的能垒,且速率控制步骤的能垒为零.由此可得,TiPc的氧还原催化能力优于已有实验结果的其他TMPcs和Pt,有可能替代Pt作为质子交换膜燃料电池(PEMFC)的氧化还原催化剂.

关键词: 过渡金属酞菁配合物, 钛酞菁配合物, 氧还原反应催化剂, 密度泛函理论, 质子交换膜燃料电池

Abstract: The research on non-platinum (Non-Pt) materials as proton exchange membrane fuel cell (PEMFC) catalyst is one of the most important activities in the corresponding fields. Transition metal phthalocyanines (TMPcs) are thought to be potential to replace Pt. Thus, the energies of absorbing O2, OH, H2O2 and H2O on FePc, CoPc, CuPc, NiPc and TiPc surfaces are investigated. It is found that the overall performance of TMPcs as catalyst is related to oxygen adsorption energy, and the higher the value is, the better the overall performance as catalyst. Based on density functional theory (DFT), the TiPc’s adsorption energies are calculated with the following results. First, the oxygen adsorption capacity of TiPc is stronger than that of the other TMPcs. Second, the O2 adsorption energy of TiPc is higher than its OH adsorption energy. Finally, the O2 adsorption energy of TiPc is also much higher than its H2O adsorption energy. Based on the analysis of TMPcs reaction mechanism, the change of Gibbs free energy of TiPc in oxygen reduction reaction is compared with that of FePc, CoPc and Pt. The theoretical calculation shows that TiPc has no obvious energy barrier during the reaction. Based on the above results, it is estimated that the oxygen reduction capacity of TiPc can be better than that of the other TMPcs and Pt, and can be used as a catalyst for PEMFC.

Key words: transition metal phthalocyanines (TMPcs), titanium phthalocyanine (TiPc), oxygen reduction catalysts, density functional theory (DFT), proton exchange membrane fuel cell (PEMFC)

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