Metal-Organic Framework-Derived Graphene Mesh: a Robust Scaffold for Highly Exposed Fe-N4 Active Sites toward an Excellent Oxygen Reduction Catalyst in Acid Media

Jingjing Li; Wei Xia; Jing Tang; Yong Gao; Cheng Jiang; Yining Jia; Tao Chen; Zhufeng Hou; Ruijuan Qi; Dong Jiang; Toru Asahi; Xingtao Xu; Tao Wang; Jianping He; Yusuke Yamauchi

doi:10.1021/jacs.2c00719

Metal-Organic Framework-Derived Graphene Mesh: a Robust Scaffold for Highly Exposed Fe-N₄ Active Sites toward an Excellent Oxygen Reduction Catalyst in Acid Media

J Am Chem Soc. 2022 Jun 1;144(21):9280-9291. doi: 10.1021/jacs.2c00719. Epub 2022 May 23.

Authors

Jingjing Li¹, Wei Xia², Jing Tang², Yong Gao¹, Cheng Jiang¹, Yining Jia², Tao Chen³, Zhufeng Hou⁴, Ruijuan Qi², Dong Jiang⁵, Toru Asahi⁵, Xingtao Xu⁶, Tao Wang¹, Jianping He¹, Yusuke Yamauchi^{5

6

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Affiliations

¹ College of Materials Science and Technology, Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China.
² School of Chemistry and Molecular Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Institute of Eco-Chongming, East China Normal University, Shanghai 200062, China.
³ Research Center for Biomedical Optics and Molecular Imaging, Shenzhen, Institutes of Advanced Technology, Chinese Academy of Sciences, 1068, Xueyuan Avenue, Shenzhen 518055, China.
⁴ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
⁵ Kagami Memorial Institute for Materials Science and Engineering, Waseda University, Nishi-Waseda 2-8-26, Shinjuku-ku, Tokyo 169-0051, Japan.
⁶ International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Ibaraki, Japan.
⁷ Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane 4072, Queensland, Australia.

PMID: 35604393
DOI: 10.1021/jacs.2c00719

Abstract

This study demonstrates a special ultrathin N-doped graphene nanomesh (NGM) as a robust scaffold for highly exposed Fe-N₄ active sites. Significantly, the pore sizes of the NGM can be elaborately regulated by adjusting the thermal exfoliation conditions to simultaneously disperse and anchor Fe-N₄ moieties, ultimately leading to highly loaded Fe single-atom catalysts (SA-Fe-NGM) and a highly exposed morphology. The SA-Fe-NGM is found to deliver a superior oxygen reduction reaction (ORR) activity in acidic media (half-wave potential = 0.83 V vs RHE) and a high power density of 634 mW cm^-2 in the H₂/O₂ fuel cell test. First-principles calculations further elucidate the possible catalytic mechanism for ORR based on the identified Fe-N₄ active sites and the pore size distribution analysis. This work provides a novel strategy for constructing highly exposed transition metals and nitrogen co-doped carbon materials (M-N-C) catalysts for extended electrocatalytic and energy storage applications.