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

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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.

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

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Konglin Wu, Shoujie Liu, Yuan Pan, Weng-Chon Cheong, Wei Zhu, Xing Cao, Rongan Shen, Wenxing Chen, Zheng Chen, Dingsheng Wang, Qing Peng, Chen Chen & Yadong Li

  2. Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, China

    Xin Chen

  3. College of Chemistry and Materials Science, Key Laboratory of Functional Molecular Solids, the Ministry of Education, Anhui Normal University, Wuhu, 241002, China

    Konglin Wu & Shoujie Liu

  4. Center for Electron Microscopy, Tianjin University of Technology, Tianjin, 300384, China

    Jun Luo

  5. National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei, 230029, China

    Wensheng Yan

  6. Beijing Synchrotron Radiation Facility (NSRF), Institute of High Energy Physics, Chinese Academy of Science, Beijing, 100049, China

    Lirong Zheng

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  1. Konglin Wu
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Correspondence to Zheng Chen or Chen Chen.

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

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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 Res. 11, 6260–6269 (2018). https://doi.org/10.1007/s12274-018-2149-y

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