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Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction

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Abstract

Nitrogen-doped graphene is a promising candidate for the replacement of noble metal-based electrocatalysts for oxygen reduction reactions (ORRs). The addition of pores and holes into nitrogen-doped graphene enhances the ORR activity by introducing abundant exposed edges, accelerating mass transfer, and impeding aggregation of the graphene sheets. Herein, we present a straightforward but effective strategy for generating porous holey nitrogen-doped graphene (PHNG) via the pyrolysis of urea and magnesium acetate tetrahydrate. Due to the combined effects of the in situ generated gases and MgO nanoparticles, the synthesized PHNGs featured not only numerous out-of-plane pores among the crumpled graphene sheets, but also interpenetrated nanoscale (5–15 nm) holes in the assembled graphene. Moreover, the nitrogen doping configurations of PHNG were optimized by post-thermal treatments at different temperatures. It was found that the overall content of pyridinic and quaternary nitrogen positively correlates with the ORR activity; in particular, pyridinic nitrogen generates the most desirable characteristics for the ORR. This work reveals new routes for the synthesis of PHNG-based materials and elucidates the contributions of various nitrogen species to ORRs.

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Acknowledgments

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21503253, 21403276 and 91545109), Natural Science Foundation of Shan-Xi province of China (No. 2015011010), and Youth Innovation Promotion Association CAS (No. 2015141).

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Authors and Affiliations

  1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China

    Li Qin, Ruimin Ding, Huixiang Wang, Jianghong Wu, Conghui Wang, Chenghua Zhang, Liancheng Wang & Baoliang Lv

  2. Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China

    Li Qin, Ruimin Ding, Huixiang Wang, Jianghong Wu, Conghui Wang, Liancheng Wang & Baoliang Lv

  3. Synfuels China Technology Co. Ltd, Beijing, 101407, China

    Chenghua Zhang

  4. State Key Laboratory of Transient Optics and Photonics, Xi’an Institute of Optics and Precision Mechanics, Chinese Academy of Sciences, Xi’an, 710119, China

    Yao Xu

  5. University of Chinese Academy of Sciences, Beijing, 100049, China

    Li Qin, Huixiang Wang, Jianghong Wu & Conghui Wang

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  1. Li Qin
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  2. Ruimin Ding
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  3. Huixiang Wang
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  8. Liancheng Wang
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  9. Baoliang Lv
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Correspondence to Liancheng Wang or Baoliang Lv.

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Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction

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Qin, L., Ding, R., Wang, H. et al. Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction. Nano Res. 10, 305–319 (2017). https://doi.org/10.1007/s12274-016-1293-5

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