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Iron polyphthalocyanine-derived ternary-balanced Fe3O4/Fe3N/Fe-N-C@PC as a high-performance electrocatalyst for the oxygen reduction reaction

聚酞菁铁驱动的三元平衡Fe3O4/Fe3N/Fe-N-C@PC作为氧还原反应高效催化剂

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Abstract

The oxygen reduction reaction (ORR) is the cornerstone reaction of the cathode in metal-air batteries; however, slow kinetics requires high-performance catalysts to promote the reaction. Polyphthalocyanine (PPc) has a typical chemical cross-linking structure and uniformly dispersed metal active sites, but its poor activity and conductivity limit its applications as an ORR catalyst. Herein, a manageable and convenient strategy is proposed to synthesize ternary ORR catalysts through the low-temperature pyrolysis of FePPc. The optimal catalyst, Fe3O4/Fe3N/Fe-N-C@PC-2.5, exhibits excellent ORR activity in alkaline solution with a half-wave potential of 0.90 V, which is significantly higher than that of commercial 20% Pt/C (0.84 V). Electrochemical tests and extended X-ray absorption fine structure spectroscopy reveal that the superior ORR activity of Fe3O4/Fe3N/Fe-N-C@PC-2.5 could be ascribed to the balance of its ternary components (i.e., Fe3O4, Fe3N, and Fe-N4 species). A Zn-air battery incorporating Fe3O4/Fe3N/Fe-N-C@PC-2.5 as an air cathodic catalyst delivers a high open-circuit voltage and peak power density. During galvanostatic discharge, the battery demonstrates a specific capacity of 815.7 mA h g−1. The facile strategy of using PPc to develop high performance composite electrocatalysts may be expanded to develop new types of catalysts in the energy field.

摘要

聚酞菁具有典型的化学交联结构和均匀分散的金属活性位点, 但是较差的活性和导电性限制了其作为氧还原催化剂的应用.本文通过热解聚酞菁铁与多孔碳的混合物制备了三元氧还原催化剂, 产物Fe3O4/Fe3N/Fe-N-C@PC-2.5在碱性溶液中的半波电势为0.90 V, 远高于市售20% Pt/C的半波电势. 电化学测试和X射线吸收精细结构相结合, 将Fe3O4/Fe3N/Fe-N-C@PC-2.5的优异氧还原活性归因于Fe3O4, Fe3N和Fe-N4三种组分的共存. 以Fe3O4/Fe3N/Fe-N-C@PC-2.5作为空气阴极催化剂的锌空气电池具有较高的开路电压和峰值功率密度. 在恒电流放电过程中, 该电池的比容量可达到815.7 mA h g−1.

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Acknowledgements

This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20200109141640095 and JCYJ20190809115413414), the National Natural Science Foundation of China (21671096 and 21905180), the Natural Science Foundation of Guangdong Province (2018A030310225), and Guangdong Provincial Key Laboratory of Energy Materials for Electric Power (2018B030322001). The authors gratefully acknowledge the support from the Center for Computational Science and Engineering and Core Research Facilities of SUSTech.

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Authors and Affiliations

  1. Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China

    Rui Hao  (郝睿), Yanping Huang  (黄燕平), Penggao Liu  (刘鹏高), Jun Yan  (颜军) & Kaiyu Liu  (刘开宇)

  2. Department of Materials Science and Engineering, Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen, 518055, China

    Rui Hao  (郝睿), Jingjing Chen  (陈晶晶), Zhenyu Wang  (王振宇), Junjun Zhang  (张钧君), Qingmeng Gan  (甘庆孟), Yanfang Wang  (王彦方), Yingzhi Li  (李英芝), Wen Luo  (罗文), Zhiqiang Wang  (王志强), Huimin Yuan  (袁惠敏), Chunliu Yan  (闫春柳), Wei Zheng  (郑薇) & Zhouguang Lu  (卢周广)

  3. Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, China

    Chen Liu  (刘琛)

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  1. Rui Hao  (郝睿)
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  2. Jingjing Chen  (陈晶晶)
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  18. Zhouguang Lu  (卢周广)
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Contributions

Hao R synthesized the materials, performed the tests, and wrote the manuscript. Chen J, Zhang J, and Huang Y provided suggestions for the manuscript. Wang ZY performed the HAADF-STEM analysis. Gan Q conducted the TEM analysis. Wang Y and Li Y collected the XANES data. Luo W performed the AFM analysis. Wang ZQ provided advice on the TOC image. Liu K, Liu C, and Lu Z reviewed and revised the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Kaiyu Liu  (刘开宇), Chen Liu  (刘琛) or Zhouguang Lu  (卢周广).

Additional information

Rui Hao is a PhD candidate at the College of Chemistry and Chemical Engineering, Central South University. His research interests include the design and synthesis of high-performance electrocatalysts for metal-air batteries.

Kaiyu Liu earned his PhD from the College of Chemistry and Chemical Engineering, Central South University, in 2003. He is now a professor at the same college and university. His research focuses on new energy-storage devices and the related materials, such as electrode materials for lithium/sodium/zinc-ion batteries and metal-air battery catalysts.

Chen Liu is an assistant professor at the College of Materials Science and Engineering, Shenzhen University. She received her PhD from the Department of Physics and Materials Science, City University of Hong Kong, in 2017. Her research interests include polymer composites/nanomaterials for electrochemical and energy applications, especially the design of solid composite electrolytes for lithium/sodium solidstate batteries.

Zhouguang Lu obtained his PhD from the City University of Hong Kong in 2009. He is now a professor at the Department of Materials Science and Engineering, Southern University of Science and Technology. His research interests include the design and synthesis of nanostructures and their applications in energy storage and conversion.

Conflict of interest

The authors have no conflict of interest to declare.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

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40843_2021_1699_MOESM1_ESM.pdf

Iron polyphthalocyanine-derived ternary-balanced Fe3O4/Fe3N/Fe-N-C@PC as a high-performance electrocatalyst for the oxygen reduction reaction

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Hao, R., Chen, J., Wang, Z. et al. Iron polyphthalocyanine-derived ternary-balanced Fe3O4/Fe3N/Fe-N-C@PC as a high-performance electrocatalyst for the oxygen reduction reaction. Sci. China Mater. 64, 2987–2996 (2021). https://doi.org/10.1007/s40843-021-1699-4

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