A comparative DFT study of oxygen reduction reaction on mononuclear and binuclear cobalt and iron phthalocyanines
- Authors: Chen X.1, Li M.1, Yu Z.1, Ke Q.1
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Affiliations:
- The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering
- Issue: Vol 90, No 12 (2016)
- Pages: 2413-2417
- Section: Structure of Matter and Quantum Chemistry
- URL: https://journals.rcsi.science/0036-0244/article/view/169042
- DOI: https://doi.org/10.1134/S0036024416120323
- ID: 169042
Cite item
Abstract
The oxygen reduction reaction (ORR) catalyzed by mononuclear and planar binuclear cobalt (CoPc) and iron phthalocyanine (FePc) catalysts is investigated in detail by density functional theory (DFT) methods. The calculation results indicate that the ORR activity of Fe-based Pcs is much higher than that of Co-based Pcs, which is due to the fact that the former could catalyze 4e- ORRs, while the latter could catalyze only 2e- ORRs from O2 to H2O2. The original high activities of Fe-based Pcs could be attributed to their high energy level of the highest occupied molecular orbital (HOMO), which could lead to the stronger adsorption energy between catalysts and ORR species. Nevertheless, the HOMO of Co-based Pcs is the ring orbital, not the 3d Co orbital, thereby inhibiting the electron transfer from metal to adsorbates. Furthermore, compared with mononuclear FePc, the planar binuclear FePc has more stable structure in acidic medium and more suitable adsorption energy of ORR species, making it a promising non-precious electrocatalyst for ORR.
About the authors
Xin Chen
The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering
Author for correspondence.
Email: chenxin830107@pku.edu.cn
China, Chengdu, 610500
Mengke Li
The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering
Email: chenxin830107@pku.edu.cn
China, Chengdu, 610500
Zongxue Yu
The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering
Email: chenxin830107@pku.edu.cn
China, Chengdu, 610500
Qiang Ke
The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering
Email: chenxin830107@pku.edu.cn
China, Chengdu, 610500