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Synthesis of N-doped Co@C/CNT materials based on ZIF-67 and their electrocatalytic performance for oxygen reduction

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Abstract

ZIF-67/CNT materials are prepared by using in situ growth method with cobalt nitrate and 2-methylimidazole (2-MI) as raw materials, polyvinyl pyrrolidone (PVP) as complexing agents. A series of N-Co@C/CNT catalysts are prepared through heating ZIF-67/CNT in N2 atmosphere. The effects of additional proportion of CNT on the catalytic performance of N-Co@C/CNT catalysts for oxygen reduction reaction (ORR) are studied. The chemical states of the materials, micro-morphology, elemental composition, and crystalline structure are analyzed by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), and X-ray diffraction (XRD). The results show that polyhedral ZIF-67 has grown on the surfaces of CNTs. After heat treatment, ZIF-67/CNT transforms to N-Co@C/CNT. The particle size of Co is 10–20 nm. N-Co@C/CNT-2.6 shows the best catalytic performance for ORR in alkaline solution with the onset potential of 0.94 V, half-wave-potential of 0.83 V, and limiting diffusion current density of 5.6 mA cm−2. The ORR on N-Co@C/CNT proceeds through a four-electron path and the yield of H2O2 is 12%, which is close to Pt/C. N-Co@C/CNT shows higher methanol-tolerant ability than Pt/C. The addition of CNT makes N-Co@C expose more active sites. CNT plays an important role in connecting different N-Co@C particles and enhancing the electron conductivity. The contents of graphitic nitrogen and pyridine nitrogen in N-Co@C/CNT-2.6 catalysts are 15.8% and 38.6%, respectively, which are higher than those in N-Co@C (7% and 34%).

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Funding

The project was supported by the key R&D and Promotion Projects (Science and Technology Key Projects) of Henan Province of China (Grant No. 202102210389 and 202102310226), the Key Scientific Research Project of the Higher Education Institutions of Henan Province of China (Grant No. 20A530001), and the 2020 Starry Sky Creative Space Incubation Project of Zhengzhou University of Light Industry of China (Grant No. 2020ZCKJ232).

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  1. Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450001, People’s Republic of China

    Haili Gao, Yunpeng Liu, Yaqiong Ma, Erchao Meng & Yong Zhang

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  1. Haili Gao
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  2. Yunpeng Liu
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  3. Yaqiong Ma
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Correspondence to Haili Gao or Yong Zhang.

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Gao, H., Liu, Y., Ma, Y. et al. Synthesis of N-doped Co@C/CNT materials based on ZIF-67 and their electrocatalytic performance for oxygen reduction. Ionics 27, 2561–2569 (2021). https://doi.org/10.1007/s11581-021-04031-y

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