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Vol. 17 (2025)

Concurrently Boosting Activity and Stability of Oxygen Reduction Reaction Catalysts via Judiciously Crafting Fe–Mn Dual Atoms for Fuel Cells

https://doi.org/10.1007/s40820-024-01580-5
Lei Zhang
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yuchen Dong
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Lubing Li
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yuchuan Shi
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yan Zhang
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Liting Wei
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Chung‑Li Dong
Department of Physics, Tamkang University, New Taipei City, Taiwan 25137, People’s Republic of China
Zhiqun Lin
Department of Chemical and Biomolecular Engineering, National University of Singapore, Engineering Drive 4, Singapore 117585, Singapore
Jinzhan Su
International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China

Corresponding Author: Jinzhan Su

j.su@mail.xjtu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 88

Abstract

The ability to unlock the interplay between the activity and stability of oxygen reduction reaction (ORR) represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells. Herein, we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe–Mn dual-metal sites on N-doped carbon (denoted (FeMn-DA)–N–C) for both anion-exchange membrane fuel cells (AEMFC) and proton exchange membrane fuel cells (PEMFC). The (FeMn-DA)–N–C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N4 and Mn-N4 sites on the carbon surface, yielded via a facile doping-adsorption-pyrolysis route. The introduction of Mn carries several advantageous attributes: increasing the number of active sites, effectively anchoring Fe due to effective electron transfer to Mn (revealed by X-ray absorption spectroscopy and density-functional theory (DFT), thus preventing the aggregation of Fe), and effectively circumventing the occurrence of Fenton reaction, thus reducing the consumption of Fe. The (FeMn-DA)–N–C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO4, respectively, as well as outstanding stability. As manifested by DFT calculations, the introduction of Mn affects the electronic structure of Fe, down-shifts the d-band Fe active center, accelerates the desorption of OH groups, and creates higher limiting potentials. The AEMFC and PEMFC with (FeMn-DA)–N–C as the cathode catalyst display high power densities of 1060 and 746 mW cm−2, respectively, underscoring their promising potential for practical applications. Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.


Highlights:
1 Fe–Mn dual-atom catalysts exhibit superior oxygen reduction reaction (ORR) activity and stability, with high half-wave potentials in both alkaline and acidic conditions.
2 Synergistic Mn incorporation effectively anchors Fe atoms, mitigates the Fenton reaction, and enhances the durability of ORR catalysts.
3 Advanced characterization and density-functional theory calculations reveal Mn-induced electronic structure modifications, promoting superior ORR kinetics and active site performance.
4 (FeMn-DA)-N-C catalysts show remarkable potential for practical fuel cell applications.

Keywords

Doping-adsorption-pyrolysis Dual-atom catalysts Oxygen reduction reaction Fuel cells
Zhang, Lei, Yuchen Dong, Lubing Li, Yuchuan Shi, Yan Zhang, Liting Wei, Chung‑Li Dong, Zhiqun Lin, and Jinzhan Su. 2024. “Concurrently Boosting Activity and Stability of Oxygen Reduction Reaction Catalysts via Judiciously Crafting Fe–Mn Dual Atoms for Fuel Cells”. Nano-Micro Letters 17 (December):88. https://doi.org/10.1007/s40820-024-01580-5.
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