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Nano Research 2018, 11(12): 6260-6269 https://doi.org/10.1007/s12274-018-2149-y
Research Article | Issue | Published: 01 August 2018

Porphyrin-like Fe-N4 sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction

Show Author's Information Konglin Wu1,3,§,  Xin Chen2,§,  Shoujie Liu1,3,  Yuan Pan1,  Weng-Chon Cheong1,  Wei Zhu1,  Xing Cao1,  Rongan Shen1,  Wenxing Chen1,  Jun Luo4,  Wensheng Yan5,  Lirong Zheng6,  Zheng Chen1( ),  Dingsheng Wang1,  Qing Peng1,  Chen Chen1( ),  Yadong Li1
Department of ChemistryTsinghua UniversityBeijing100084China
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline MaterialsDepartment of ChemistryUniversity of Science and Technology BeijingBeijing100083China
College of Chemistry and Materials ScienceKey Laboratory of Functional Molecular Solidsthe Ministry of EducationAnhui Normal UniversityWuhu241002China
Center for Electron MicroscopyTianjin University of TechnologyTianjin300384China
National Synchrotron Radiation Laboratory (NSRL)University of Science and Technology of ChinaHefei230029China
Beijing Synchrotron Radiation Facility (NSRF)Institute of High Energy PhysicsChinese Academy of ScienceBeijing100049China

§Konglin Wu and Xin Chen contributed equally to this work.

Keywords:
single-atom catalyst, heteroatom codoping, porous materials, oxygen reduction, electrocatalysis
Cite this article:
Wu K, Chen X, Liu S, et al. Porphyrin-like Fe-N4 sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction. Nano Research, 2018, 11(12): 6260-6269. https://doi.org/10.1007/s12274-018-2149-y
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Abstract Full text Electronic supplementary material About this article

We developed a strategy based on coordination polymer to synthesize singleatom site Fe/N and S-codoped hierarchical porous carbon (Fe1/N, S-PC). The as-obtained Fe1/N, S-PC exhibited superior oxygen reduction reaction (ORR) performance with a half-wave potential (E1/2, 0.904 V vs. RHE) that was better than that of commercial Pt/C (E1/2, 0.86 V vs. RHE), single-atom site Fe/N-doped hierarchical porous carbon (Fe1/N-PC) without S-doped (E1/2, 0.85 V vs. RHE), and many other nonprecious metal catalysts in alkaline medium. Moreover, the Fe1/N, S-PC revealed high methanol tolerance and firm stability. The excellent electrocatalytic activity of Fe1/N, S-PC is attributed to the synergistic effects from the atomically dispersed porphyrin-like Fe-N4 active sites, the heteroatom codoping (N and S), and the hierarchical porous structure in the carbon materials. The calculation based on density functional theory further indicates that the catalytic performance of Fe1/N, S-PC is better than that of Fe1/N-PC owing to the sulfur doping that yielded different rate-determining steps.


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Electronic supplementary material
About this article

Porphyrin-like Fe-N4 sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction

Show Author's information Konglin Wu1,3,§, Xin Chen2,§, Shoujie Liu1,3, Yuan Pan1, Weng-Chon Cheong1, Wei Zhu1, Xing Cao1, Rongan Shen1, Wenxing Chen1, Jun Luo4, Wensheng Yan5, Lirong Zheng6, Zheng Chen1( ), Dingsheng Wang1, Qing Peng1, Chen Chen1( ), Yadong Li1
Department of ChemistryTsinghua UniversityBeijing100084China
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline MaterialsDepartment of ChemistryUniversity of Science and Technology BeijingBeijing100083China
College of Chemistry and Materials ScienceKey Laboratory of Functional Molecular Solidsthe Ministry of EducationAnhui Normal UniversityWuhu241002China
Center for Electron MicroscopyTianjin University of TechnologyTianjin300384China
National Synchrotron Radiation Laboratory (NSRL)University of Science and Technology of ChinaHefei230029China
Beijing Synchrotron Radiation Facility (NSRF)Institute of High Energy PhysicsChinese Academy of ScienceBeijing100049China

§Konglin Wu and Xin Chen contributed equally to this work.

Abstract

We developed a strategy based on coordination polymer to synthesize singleatom site Fe/N and S-codoped hierarchical porous carbon (Fe1/N, S-PC). The as-obtained Fe1/N, S-PC exhibited superior oxygen reduction reaction (ORR) performance with a half-wave potential (E1/2, 0.904 V vs. RHE) that was better than that of commercial Pt/C (E1/2, 0.86 V vs. RHE), single-atom site Fe/N-doped hierarchical porous carbon (Fe1/N-PC) without S-doped (E1/2, 0.85 V vs. RHE), and many other nonprecious metal catalysts in alkaline medium. Moreover, the Fe1/N, S-PC revealed high methanol tolerance and firm stability. The excellent electrocatalytic activity of Fe1/N, S-PC is attributed to the synergistic effects from the atomically dispersed porphyrin-like Fe-N4 active sites, the heteroatom codoping (N and S), and the hierarchical porous structure in the carbon materials. The calculation based on density functional theory further indicates that the catalytic performance of Fe1/N, S-PC is better than that of Fe1/N-PC owing to the sulfur doping that yielded different rate-determining steps.

Keywords: single-atom catalyst, heteroatom codoping, porous materials, oxygen reduction, electrocatalysis

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Acknowledgements

Publication history

Received: 21 April 2018
Revised: 03 July 2018
Accepted: 09 July 2018
Published: 01 August 2018
Issue date: June 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

This work was supported by China Ministry of Science and Technology under Contract of 2016YFA (0202801), the National Natural Science Foundation of China (Nos. 21521091, 21390393, U1463202, 21573119, 21590792, and 21501004). We thanks for the help from the Beijing Synchrotron Radiation Facility (BSRF) and National Synchrotron Radiation Laboratory (NSRL) in characterizations.

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