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A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts

Author

Listed:
  • Travis Marshall-Roth

    (Massachusetts Institute of Technology)

  • Nicole J. Libretto

    (Purdue University
    Chemical Science and Engineering Division, Argonne National Laboratory, Argonne)

  • Alexandra T. Wrobel

    (Harvard University)

  • Kevin J. Anderton

    (Harvard University)

  • Michael L. Pegis

    (Massachusetts Institute of Technology)

  • Nathan D. Ricke

    (Massachusetts Institute of Technology)

  • Troy Van Voorhis

    (Massachusetts Institute of Technology)

  • Jeffrey T. Miller

    (Purdue University
    Chemical Science and Engineering Division, Argonne National Laboratory, Argonne)

  • Yogesh Surendranath

    (Massachusetts Institute of Technology)

Abstract

Iron- and nitrogen-doped carbon (Fe-N-C) materials are leading candidates to replace platinum catalysts for the oxygen reduction reaction (ORR) in fuel cells; however, their active site structures remain poorly understood. A leading postulate is that the iron-containing active sites exist primarily in a pyridinic Fe-N4 ligation environment, yet, molecular model catalysts generally feature pyrrolic coordination. Herein, we report a molecular pyridinic hexaazacyclophane macrocycle, (phen2N2)Fe, and compare its spectroscopic, electrochemical, and catalytic properties for ORR to a typical Fe-N-C material and prototypical pyrrolic iron macrocycles. N 1s XPS and XAS signatures for (phen2N2)Fe are remarkably similar to those of Fe-N-C. Electrochemical studies reveal that (phen2N2)Fe has a relatively high Fe(III/II) potential with a correlated ORR onset potential within 150 mV of Fe-N-C. Unlike the pyrrolic macrocycles, (phen2N2)Fe displays excellent selectivity for four-electron ORR, comparable to Fe-N-C materials. The aggregate spectroscopic and electrochemical data demonstrate that (phen2N2)Fe is a more effective model of Fe-N-C active sites relative to the pyrrolic iron macrocycles, thereby establishing a new molecular platform that can aid understanding of this important class of catalytic materials.

Suggested Citation

  • Travis Marshall-Roth & Nicole J. Libretto & Alexandra T. Wrobel & Kevin J. Anderton & Michael L. Pegis & Nathan D. Ricke & Troy Van Voorhis & Jeffrey T. Miller & Yogesh Surendranath, 2020. "A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts," Nature Communications, Nature, vol. 11(1), pages 1-14, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-18969-6
    DOI: 10.1038/s41467-020-18969-6
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    Cited by:

    1. Beibei Li & Ruonan Ma & Lei Chen & Caiyu Zhou & Yu-Xiao Zhang & Xiaonan Wang & Helai Huang & Qikun Hu & Xiaobo Zheng & Jiarui Yang & Mengjuan Shao & Pengfei Hao & Yanfen Wu & Yizhen Che & Chang Li & T, 2023. "Diatomic iron nanozyme with lipoxidase-like activity for efficient inactivation of enveloped virus," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Kang Liu & Junwei Fu & Yiyang Lin & Tao Luo & Ganghai Ni & Hongmei Li & Zhang Lin & Min Liu, 2022. "Insights into the activity of single-atom Fe-N-C catalysts for oxygen reduction reaction," Nature Communications, Nature, vol. 13(1), pages 1-8, December.

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