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Vol. 15 (2023)

Engineering Fe-N4 Electronic Structure with Adjacent Co-N2C2 and Co Nanoclusters on Carbon Nanotubes for Efficient Oxygen Electrocatalysis

https://doi.org/10.1007/s40820-023-01195-2
Mingjie Wu
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, People’s Republic of China
Xiaohua Yang
Department of Electrical Engineering, École de Technologie Supérieure (ÉTS), Montreal, QC H3C 1K3, Canada
Xun Cui
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, People’s Republic of China
Ning Chen
Canadian Light Source (CLS), 44 Innovation Boulevard, Saskatoon, SK S7N 2V3, Canada
Lei Du
Institut National de la Recherche Scientifique (INRS), Center Énergie Matériaux Télécommunications, Varennes, QC J3X 1P7, Canada
Mohamed Cherif
Institut National de la Recherche Scientifique (INRS), Center Énergie Matériaux Télécommunications, Varennes, QC J3X 1P7, Canada
Fu‑Kuo Chiang
National Institute of Low-Carbon-and-Clean-Energy, Beijing 102211, People’s Republic of China
Yuren Wen
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, People’s Republic of China
Amir Hassanpour
Institut National de la Recherche Scientifique (INRS), Center Énergie Matériaux Télécommunications, Varennes, QC J3X 1P7, Canada
François Vidal
Institut National de la Recherche Scientifique (INRS), Center Énergie Matériaux Télécommunications, Varennes, QC J3X 1P7, Canada
Sasha Omanovic
Department of Chemical Engineering, McGill University, 3610 University Street, Montreal, QC H3A 0C5, Canada
Yingkui Yang
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, People’s Republic of China
Shuhui Sun
Institut National de la Recherche Scientifique (INRS), Center Énergie Matériaux Télécommunications, Varennes, QC J3X 1P7, Canada
Gaixia Zhang
Department of Electrical Engineering, École de Technologie Supérieure (ÉTS), Montreal, QC H3C 1K3, Canada

Corresponding Author: Gaixia Zhang

gaixia.zhang@etsmtl.ca

Nano-Micro Letters, Vol. 15 (2023), Article Number: 232

Abstract

Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement. Unlike the previously reported single-atom or dual-atom configurations, we designed a new type of binary-atom catalyst, through engineering Fe-N4 electronic structure with adjacent Co-N2C2 and nitrogen-coordinated Co nanoclusters, as oxygen electrocatalysts. The resultant optimized electronic structure of the Fe-N4 active center favors the binding capability of intermediates and enhances oxygen reduction reaction (ORR) activity in both alkaline and acid conditions. In addition, anchoring M–N–C atomic sites on highly graphitized carbon supports guarantees of efficient charge- and mass-transports, and escorts the high bifunctional catalytic activity of the entire catalyst. Further, through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses, the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed. This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior. It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M–N–C catalysts.


Highlights:
1 Engineering Fe-N4 electronic structure with adjacent Co-N2C2 and Co sub-nanoclusters to optimize the electronic structure of the Fe-N4 active center is first demonstrated.
2 Electrochemical studies reveal that the amorphous carbon corrosion leads to significantly increased charge- and mass-transport resistances.
3 The operando X-ray absorption spectroscopy allows an investigation of the effect of highly oxidative environments on electrochemical behavior.

Keywords

Atomically dispersed Fe–N–C catalysts ORR/OER Rechargeable zinc-air battery Fuel cells
Wu, Mingjie, Xiaohua Yang, Xun Cui, Ning Chen, Lei Du, Mohamed Cherif, Fu‑Kuo Chiang, Yuren Wen, Amir Hassanpour, François Vidal, Sasha Omanovic, Yingkui Yang, Shuhui Sun, and Gaixia Zhang. 2023. “Engineering Fe-N4 Electronic Structure With Adjacent Co-N2C2 and Co Nanoclusters on Carbon Nanotubes for Efficient Oxygen Electrocatalysis”. Nano-Micro Letters 15 (October):232. https://doi.org/10.1007/s40820-023-01195-2.
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