A direct four-electron process on Fe–N3 doped graphene for the oxygen reduction reaction: a theoretical perspective

Xiaowan Bai; Erjun Zhao; Wencheng Wang; Ying Wang; Kai Li; Lin Lin; Jucai Yang; He Sun; Zhijian Wu

doi:10.1039/C7RA03157B

A direct four-electron process on Fe–N₃ doped graphene for the oxygen reduction reaction: a theoretical perspective†

Xiaowan Bai,^ac Erjun Zhao,

*^a Wencheng Wang,*^b Ying Wang,^c Kai Li,^c Lin Lin,^a Jucai Yang,^d He Sun^e and Zhijian Wu*^c

Author affiliations

* Corresponding authors

^a College of Science, Inner Mongolia Key Laboratory of Theoretical Chemistry Simulation, Inner Mongolia University of Technology, Hohhot 010051, P. R. China
E-mail: ejzhao@yahoo.com

^b Radiotherapy Laboratory, Jilin Cancer Hospital, Changchun 130012, P. R. China
E-mail: wencheng.w@163.com

^c State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China
E-mail: zjwu@ciac.ac.cn

^d School of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot 010051, P. R. China

^e The Computing Center of Jilin Province, Changchun 130012, P. R. China

Abstract

As one of the potential candidates for electrocatalysis, non-precious transition metal and nitrogen co-doped graphene has attracted extensive attention in recent years. A deep understanding of the oxygen reduction reaction (ORR) mechanism including the specific active sites and reaction pathways will contribute to the further enhancement of the catalytic activity. In this study, the reaction mechanism for ORR on Fe–N₃ doped graphene (Fe–N₃-Gra) is investigated theoretically. Our results show that Fe–N₃-Gra is thermodynamically stable. The ORR elementary reactions take place within a small region around the Fe–N₃ moiety and its adjacent six C atoms. HOOH does not exist on the catalyst surface, indicating a direct four-electron process for Fe–N₃-Gra. The kinetically most favorable pathway is O₂ hydrogenation, in which the formation of the second H₂O is the rate-determining step with an energy barrier of 0.87 eV. This value is close to 0.80 eV for pure Pt, suggesting that Fe–N₃-Gra could be a potential electrocatalyst. Free energy changes at different electrode potentials are also discussed.

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Article information

DOI: https://doi.org/10.1039/C7RA03157B
Article type: Paper
Submitted: 17 Mar 2017
Accepted: 24 Apr 2017
First published: 03 May 2017
This article is Open Access

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RSC Adv., 2017,7, 23812-23819

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A direct four-electron process on Fe–N₃ doped graphene for the oxygen reduction reaction: a theoretical perspective

X. Bai, E. Zhao, W. Wang, Y. Wang, K. Li, L. Lin, J. Yang, H. Sun and Z. Wu, RSC Adv., 2017, 7, 23812 DOI: 10.1039/C7RA03157B

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