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SCIENCE CHINA Materials, Volume 61, Issue 10: 1305-1313(2018) https://doi.org/10.1007/s40843-018-9269-x

Constrained-volume assembly of organometal confined in polymer to fabricate multi-heteroatom doped carbon for oxygen reduction reaction

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  • ReceivedMar 5, 2018
  • AcceptedMar 31, 2018
  • PublishedApr 28, 2018

Abstract

The design and preparation of non-precious metal and carbon-based nanocomposites are critical to the development of efficient catalysts for technologies ranging from water splitting to fuel cell. Here, we present a constrained-volume self-assembly process for the one-step continuous precipitation-induced formation of soft colloidal particles, in which hydrophobic organoferrous compound, (Ph3P)2Fe(CO)3, is encapsulated within poly(styrene-co-acrylonitrile) nanoparticles (NPs). The protective and confining polymer matrix ensures uniform carbonization and dispersion of (Ph3P)2Fe(CO)3 within a carbon matrix after a pyrolysis process. The obtained carbon NPs are successfully co-doped with Fe, P and N with a relatively high surface area of ~380 m2 g−1. The Fe-P-N-doped carbon catalyst exhibits high catalytic performance and stability toward oxygen reduction reaction in both alkaline and acidic electrolytes via a favorable four-electron pathway. Meanwhile, the catalytic capability of Fe-P-N-doped carbon can be tailored by the tunable nanostructures.


Funded by

the National Natural Science Foundation of China(21774095)

Shanghai Municipal Natural Science Foundation(17ZR1432200)

the Fundamental Research Funds for the Central Universities(0400219376)

and the start-up funding from Tongji University and the Young Thousand Talented Program.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21774095), Shanghai Municipal Natural Science Foundation (17ZR1432200), the Fundamental Research Funds for the Central Universities (0400219376), and the start-up funding from Tongji University and the Young Thousand Talented Program.


Interest statement

The authors declare no conflict of interest.


Contributions statement

Liu R proposed the research and guided the whole project; Li C performed the experiments and wrote the manuscript; Zhao J and Priestley RD helped analyze the data. All authors contributed to the general discussion and reviewed the manuscript.


Author information

Congling Li received his PhD degree in chemistry from East China Normal University in 2017. In the same year, she carried out her postdoctoral research at Tongji University.


Rui Liu received his PhD degree in chemistry from the University of California, Riverside in 2010. He carried out his postdoctoral research at Oak Ridge National Laboratory from 2011 to 2012. In 2012–2015, he was a postdoctoral associate at Princeton University. In 2015, he was selected in Young Thousand Talented programe and joined Tongji University as a professor. His research interests include polymer self-assembly, carbon nanoparticles and energy applications.


Supplement

Supplementary information

Experimental details are available in the online version of the paper.


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  • Figure 1

    Schematic illustration of constrained-volume self-assembled (Ph3P)2Fe(CO)3@PS-c-PAN NPs and conversion into Fe-P-N-doped carbon materials.

  • Figure 2

    TEM images of (a) pure PS-c-PAN NPs; (b) (Ph3P)2Fe(CO)3@PS-c-PAN NPs. (c) STEM and elemental mapping of (Ph3P)2Fe(CO)3@PS-c-PAN NPs.

  • Figure 3

    TEM images of (a) FNP-5, (b) FNP-3 and (c) FNP-1; (d) corresponding HRTEM images of FNP-5.

  • Figure 4

    (a) Raman spectra of FNP-5 (lack line) and FNP-0 (red line); (b) N2 sorption isotherm and pore size distribution (inset) of FNP-5.

  • Figure 5

    Deconvoluted high resolution XPS of FNP-5: (a) Fe 2p, (b) N 1s and (c) P 2p; (d) a simplified model of Fe-P-N doped carbon (green ball: N; blue ball: P; red ball: Fe; black ball: C).

  • Figure 6

    CV curves of the prepared Fe-P-N-doped carbon in O2-saturated (a) 0.1 mol L−1 KOH and (d) 0.1 mol L−1 HClO4. RRDE polarization curves for Fe-P-N-doped carbon and commercial Pt/C at 1,600 rpm in O2-saturated (b) 0.1 mol L−1 KOH and (e) 0.1 mol L−1 HClO4. Calculated peroxide yields and theelectron transfer number based on the corresponding RRDE polarization curves in O2-saturated(c) 0.1 mol L−1 KOH and (f) 0.1 mol L−1 HClO4.

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