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The key roles of trace iron for nitrogen, sulfur dual-doped carbon nanospheres as high efficient oxygen reduction catalyst

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Abstract

Trace iron (Fe) has been found to be critical for improving the catalytic activity of heteroatom-doped carbon materials for oxygen reduction reaction (ORR). However, the exact roles played by the trace Fe in the catalysts have not been studied in detail. In this study, nitrogen (N) and sulfur (S) dual-doped carbon nanospheres were synthesized with and without trace Fe addition, named NSFeDC and NSDC, respectively. NSFeDC showed obviously stronger catalytic activity for ORR than NSDC. The microstructures of these two catalysts were characterized comprehensively. After adding the trace Fe, the contents of N and S in NSFeDC were 8.1 and 3.3 times higher than those in NSDC. The functional group composition analysis demonstrated that one part of the increased N/S formed the chemical bond of Fe–N and Fe–S, and the other part was involved in the abundant extra formation of metal-free N/S-based active site, such as pyridinic N and –C–S–C–. The underlying mechanism is that the trace iron not only participated itself in constructing the active sites, but also served as the catalyst for the formation of N/S-based active sites. The comparison between the TEM images of NSDC and NSFeDC clearly showed that the size of the nanosphere increased after adding the trace Fe. This was probably because the iron atom connected two separate carbon groups together by bonding with the nitrogen atoms. Besides the enlarged particle size, the surface area of NSFeDC decreased by nearly one half compared to that of NSDC.

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Acknowledgement

This work was supported by the National Natural Science Foundation of China [No. 51408469]; the Key Laboratory of Education Department of Shanxi province [15JS046]; and Xi’an University of Architecture and Technology [QN1416 and RC1366].

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Authors and Affiliations

  1. School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an, 710055, People’s Republic of China

    Xinxin Shi, Jiaona Zhang & Tinglin Huang

  2. Key Laboratory of Northwest Resource, Environment and Ecology, MOE, Xi’an University of Architecture and Technology, Xi’an, 710055, People’s Republic of China

    Xinxin Shi, Jiaona Zhang & Tinglin Huang

  3. Shanxi Key Laboratory of Environmental Engineering, Xi’an University of Architecture and Technology, Xi’an, 710055, People’s Republic of China

    Xinxin Shi, Jiaona Zhang & Tinglin Huang

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  1. Xinxin Shi
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Correspondence to Xinxin Shi.

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Shi, X., Zhang, J. & Huang, T. The key roles of trace iron for nitrogen, sulfur dual-doped carbon nanospheres as high efficient oxygen reduction catalyst. J Mater Sci 53, 1404–1413 (2018). https://doi.org/10.1007/s10853-017-1605-5

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