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Nano Research 2021, 14(12): 4512-4519 https://doi.org/10.1007/s12274-021-3823-z
Research Article | Issue | Published: 16 September 2021

Structural revolution of atomically dispersed Mn sites dictates oxygen reduction performance

Show Author's Information Zhengkun Yang1,3,§( ),  Xiaolin Wang2,§,  Mengzhao Zhu1,§,  Xinyan Leng3,  Wenxing Chen4,  Wenyu Wang1,  Qian Xu5,  Li-Ming Yang2( ),  Yuen Wu1( )
School of Chemistry and Materials Science, iChEM, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education; Hubei Key Laboratory of Materials Chemistry and Service Failure; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials (Anhui University), Ministry of Education, Anhui Graphene Engineering Laboratory, Anhui University, Hefei 230601, China
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
National Synchrotron Radiation Laboratory (NSRL), Hefei 230026, China

Keywords:
fuel cells, thermal diffusion, coordination repairing, single-atom manganese, oxygen reduction catalysis
Topics:
Fuel cells
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Yang Z, Wang X, Zhu M, et al. Structural revolution of atomically dispersed Mn sites dictates oxygen reduction performance. Nano Research, 2021, 14(12): 4512-4519. https://doi.org/10.1007/s12274-021-3823-z
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Abstract Full text Electronic supplementary material About this article

An efficient preparation and local coordination environment regulation of isolated single-atom sites catalysts (ISASC) for improved activity is still challenging. Herein, we develop a solid phase thermal diffusion strategy to synthesize Mn ISASC on highly uniform nitrogen-doped carbon nanotubes by employing MnO2 nanowires@ZIF-8 core-shell structure. Under high-temperature, the Mn species break free from core-MnO2 lattice, which will be trapped by carbon defects derived from shell-ZIF-8 carbonization, and immobilized within carbon substrate. Furthermore, the poly-dispersed Mn sites with two nitrogen-coordinated centers can be controllably renovated into four-nitrogen-coordinated Mn sites using NH3 treatment technology. Both experimental and computational investigations indicate that the symmetric coordinated Mn sites manifest outstanding oxygen reduction activity and superior stability in alkaline and acidic solutions. This work not only provides efficient way to regulate the coordination structure of ISASC to improve catalytic performance but also paves the way to reveal its significant promise for commercial application.


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Electronic supplementary material
About this article

Structural revolution of atomically dispersed Mn sites dictates oxygen reduction performance

Show Author's information Zhengkun Yang1,3,§( ), Xiaolin Wang2,§, Mengzhao Zhu1,§, Xinyan Leng3, Wenxing Chen4, Wenyu Wang1, Qian Xu5, Li-Ming Yang2( ), Yuen Wu1( )
School of Chemistry and Materials Science, iChEM, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education; Hubei Key Laboratory of Materials Chemistry and Service Failure; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials (Anhui University), Ministry of Education, Anhui Graphene Engineering Laboratory, Anhui University, Hefei 230601, China
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
National Synchrotron Radiation Laboratory (NSRL), Hefei 230026, China

Abstract

An efficient preparation and local coordination environment regulation of isolated single-atom sites catalysts (ISASC) for improved activity is still challenging. Herein, we develop a solid phase thermal diffusion strategy to synthesize Mn ISASC on highly uniform nitrogen-doped carbon nanotubes by employing MnO2 nanowires@ZIF-8 core-shell structure. Under high-temperature, the Mn species break free from core-MnO2 lattice, which will be trapped by carbon defects derived from shell-ZIF-8 carbonization, and immobilized within carbon substrate. Furthermore, the poly-dispersed Mn sites with two nitrogen-coordinated centers can be controllably renovated into four-nitrogen-coordinated Mn sites using NH3 treatment technology. Both experimental and computational investigations indicate that the symmetric coordinated Mn sites manifest outstanding oxygen reduction activity and superior stability in alkaline and acidic solutions. This work not only provides efficient way to regulate the coordination structure of ISASC to improve catalytic performance but also paves the way to reveal its significant promise for commercial application.

Keywords: fuel cells, thermal diffusion, coordination repairing, single-atom manganese, oxygen reduction catalysis

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Publication history
Copyright
Acknowledgements

Publication history

Received: 14 July 2021
Revised: 13 August 2021
Accepted: 16 August 2021
Published: 16 September 2021
Issue date: December 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This work was supported by the National Key R&D Program of China 2017YFA (Nos. 0208300 and 0700104), the National Natural Science Foundation of China (Nos. 21671180, 21802132, 22073033, 21673087, 21873032, and 21903032), startup fund (Nos. 2006013118 and 3004013105) from Huazhong University of Science and Technology, the Fundamental Research Funds for the Central Universities (2019kfyRCPY116), and the Innovation and Talent Recruitment Base of New Energy Chemistry and Device (B21003). The work was carried out at the LvLiang Cloud Computing Center of China, and the calculations were performed on TianHe-2. The computing work in this paper is supported by the public computing service platform provided by Network and Computing Center of HUST. We thank the photoemission endstations BL1W1B in Beijing Synchrotron Radiation Facility (BSRF), BL14W1 in Shanghai Synchrotron Radiation Facility (SSRF), BL10B and BL11U in National Synchrotron Radiation Laboratory (NSRL) for the help in characterizations.

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