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MOF-derived Co nanoparticles embedded in N,S-codoped carbon layer/MWCNTs for efficient oxygen reduction in alkaline media

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Abstract

The hydrothermal reaction of cobalt salt in the presence of 4-pyridyl-tetrathiafulvalene-4-pyridyl (4-py-TTF-4-py) and terephthalic acid (PTA) has been employed for the preparation of a novel metal–organic framework (MOF), i.e., (4-py-TTF-4-py)2M2(PTA)4 (M = Co2+). The obtained MOF is then used as a starting material for the synthesis of Co nanoparticles embedded in N,S-codoped carbon layer and supported on multi-walled carbon nanotubes (Co@NSC/MWCNTs) through the high-temperature calcination. Specifically, the calcination leads to the formation of N,S-codoped carbon-coated Co nanoparticles with simultaneous growth on the MWCNTs due to decomposition of the MOF. When used as the electrocatalyst, the Co@NSC/MWCNTs are found to have a higher activity for the oxygen reduction reaction (ORR) and follow a four-electron pathway. The catalytic activity of the Co@NSC/MWCNTs is much higher than that of the pure MWCNTs and the MOFs/MWCNTs. Although the Co@NSC/MWCNTs still exhibit slightly higher overpotential for the ORR, it is indeed more kinetically facile than the commercial Pt/C catalyst, as demonstrated by its higher limiting current density and lower Tafel slope. Additionally, the Co@NSC/MWCNTs also show superior stability and better tolerance to methanol crossover and CO poisoning, compared with those of the commercial Pt/C catalyst. These results strongly suggest that the Co@NSC/MWCNTs could be used as one of the most promising ORR electrocatalysts for the ORR with great potential to replace the Pt/C. The work present here opens up a new route for the design of carbon-integrated ORR electrocatalysts with high performance from a great number of available and yet rapidly growing MOFs.

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Funding

This work is supported by the Chinese National Natural Science Foundation (Nos. U1532139 and 21476156), the Ningbo Natural Science Foundation (No. 2017A610059), Fundamental Research Funds for the Central Universities of SCUT (No.2018ZD25), the Guangdong Provincial Natural Science Foundation (No. 2017A030313092), and the Guangdong Innovative and Entepreneurial Research Team Program (No. 2014ZT05N200).

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Authors and Affiliations

  1. Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan, 030024, China

    Shasha Li & **aogang Hao

  2. Department of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, 315211, Zhejiang, China

    Shasha Li, Zhongqing Jiang, Xunwen **ao, Weiheng Chen & **aoning Tian

  3. Department of Physics, Key Laboratory of ATMMT Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Zhongqing Jiang

  4. Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, College of Environment and Energy, South China University of Technology, Guangzhou, 510006, China

    Zhong-Jie Jiang

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  1. Shasha Li
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  4. Weiheng Chen
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Correspondence to Zhongqing Jiang, Xunwen **ao or **aogang Hao.

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Li, S., Jiang, Z., **ao, X. et al. MOF-derived Co nanoparticles embedded in N,S-codoped carbon layer/MWCNTs for efficient oxygen reduction in alkaline media. Ionics 25, 785–796 (2019). https://doi.org/10.1007/s11581-018-2775-0

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