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Vol. 12 (2020)

Secondary-Atom-Doping Enables Robust Fe–N–C Single-Atom Catalysts with Enhanced Oxygen Reduction Reaction

https://doi.org/10.1007/s40820-020-00502-5
Xin Luo
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Xiaoqian Wei
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Hengjia Wang
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Wenling Gu
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China
Takuma Kaneko
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan
Yusuke Yoshida
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan
Xiao Zhao
Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182‑8585, Japan HIGHLIGHTS • Secondary-atom-doped strategy was proposed to synthesize single-atom electrocatalyst. • The increase in both the density of active sites and their intrinsic activity was achieved simultaneously. • The resultant single-atom catalyst shows outstanding ORR activity in acidic media. ABSTRACT Single-atom catalysts (SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis. However, a large room for improving their activity and durability remains. Herein, we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy. Upon the secondary doping, the density and coordination environment of active sites can be efficiently tuned, enabling the simultaneous improvement in the number and reactivity of the active site. Besides, structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously. Due to the beneficial microstructure and abundant highly active FeN5 moieties resulting from the secondary doping, the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media. This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices. KEYWORDS Single-atom catalysts; Fe–N–C catalysts; Doping; Porous nanostructures; Oxygen reduction reaction dicyandiamide Fe3+ O2 H2O H2O
Chengzhou Zhu
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, People’s Republic of China

Corresponding Author: Chengzhou Zhu

czzhu@mail.ccnu.edu.cn

Nano-Micro Letters, Vol. 12 (2020), Article Number: 163

Abstract

Single-atom catalysts (SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis. However, a large room for improving their activity and durability remains. Herein, we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy. Upon the secondary doping, the density and coordination environment of active sites can be efficiently tuned, enabling the simultaneous improvement in the number and reactivity of the active site. Besides, structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously. Due to the beneficial microstructure and abundant highly active FeN5 moieties resulting from the secondary doping, the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media. This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices.


Highlights:


1 Secondary-atom-doped strategy was proposed to synthesize single-atom electrocatalyst.
2 The increase in both the density of active sites and their intrinsic activity was achieved simultaneously.
3 The resultant single-atom catalyst shows outstanding ORR activity in acidic media.

Keywords

Single-atom catalysts Fe–N–C catalysts Doping Porous nanostructures Oxygen reduction reaction
Luo, Xin, Xiaoqian Wei, Hengjia Wang, Wenling Gu, Takuma Kaneko, Yusuke Yoshida, Xiao Zhao, and Chengzhou Zhu. 2020. “Secondary-Atom-Doping Enables Robust Fe–N–C Single-Atom Catalysts With Enhanced Oxygen Reduction Reaction”. Nano-Micro Letters 12 (August):163. https://doi.org/10.1007/s40820-020-00502-5.
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