A theoretical study of atomically dispersed MN4/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction

Hao Xu; Dan Wang; Peixia Yang; Anmin Liu; Ruopeng Li; Yun Li; Lihui Xiao; Jinqiu Zhang; Maozhong An

doi:10.1039/D0CP04676K

A theoretical study of atomically dispersed MN₄/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction†

Hao Xu,^a Dan Wang,^a Peixia Yang,

*^a Anmin Liu,*^b Ruopeng Li,^a Yun Li,^a Lihui Xiao,^a Jinqiu Zhang^a and Maozhong An^a

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* Corresponding authors

^a MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China
E-mail: yangpeixia@hit.edu.cn

^b State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China
E-mail: liuanmin@dlut.edu.cn

Abstract

Carbon-based, non-noble metal catalysts for the oxygen reduction reaction (ORR) are crucial for the large-scale application of metal–air batteries and fuel cells. Density functional theory calculations were performed to explore the potential of atomically dispersed MN₄/C (M = Fe or Mn) as an ORR catalyst in an acidic electrolyte and the ORR mechanism on MN₄/C was systematically studied. The results indicated MN₄ as the active site of MN₄/C and a four-electron OOH transformation pathway as the preferred ORR mechanism on the MN₄/C surface. The Gibbs free energy diagram showed that the rate-determining step of the FeN₄/C and MnN₄/C catalysts is the formation of the second H₂O molecule and OOH*, respectively. FeN₄/C exhibited higher thermodynamic limiting potential (0.79 V) and, thus, higher ORR activity than MnN₄/C (0.52 V) in an acidic environment; its excellent catalytic performance is due to the nice electron structure and adsorption properties of the FeN₄ site. Therefore, this work demonstrates that atomically dispersed MN₄/C is a promising catalyst for the ORR.

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DOI: https://doi.org/10.1039/D0CP04676K
Article type: Paper
Submitted: 05 Sep 2020
Accepted: 20 Nov 2020
First published: 23 Nov 2020

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Phys. Chem. Chem. Phys., 2020,22, 28297-28303

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A theoretical study of atomically dispersed MN₄/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction

H. Xu, D. Wang, P. Yang, A. Liu, R. Li, Y. Li, L. Xiao, J. Zhang and M. An, Phys. Chem. Chem. Phys., 2020, 22, 28297 DOI: 10.1039/D0CP04676K

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Physical Chemistry Chemical Physics

A theoretical study of atomically dispersed MN₄/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction†

Abstract

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A theoretical study of atomically dispersed MN₄/C (M = Fe or Mn) as a high-activity catalyst for the oxygen reduction reaction

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Physical Chemistry Chemical Physics