Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction

Zitolo, Andrea and Ranjbar-Sahraie, Nastaran and Mineva, Tzonka and Li, Jingkun and Jia, Qingying and Stamatin, Serban and Harrington, George F. and Lyth, Stephen Mathew and Krtil, Petr and Mukerjee, Sanjeev and Fonda, Emiliano and Jaouen, Frédéric (2017) Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications, 8 (1). pp. 1-11. 957. ISSN 2041-1723 (https://doi.org/10.1038/s41467-017-01100-7)

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Abstract

Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.

  • Item type:Article
    ID code:85400
    Dates:
    Date
    Event
    16 October 2017
    Published
    17 August 2017
    Accepted
    22 February 2017
    Submitted
    Notes:Funding Information: This research was supported by ANR under contract 2011 CHEX 004 01 and by the Project ‘PEMFC-SUDOE’ -SOE1/P1/E0293 which is co-financed by the European Regional Development Fund in the framework of the Interreg Sudoe programme. We also acknowledge Synchrotron SOLEIL (Gif-sur Yvette, France) for provision of synchrotron radiation facilities at beamline SAMBA (proposal numbers 20120701 and 20150913), Valérie Briois for valuable discussions and Álvaro Reyes-Carmona (formerly at Université Montpellier, now at ICIQ, Spain) for sharing the benchmark IrO2 polarization curve. Publisher Copyright: © 2017 The Author(s). Zitolo, A., Ranjbar-Sahraie, N., Mineva, T. et al. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nat Commun 8, 957 (2017). https://doi.org/10.1038/s41467-017-01100-7
    Subjects:Science > Chemistry
    Department:Faculty of Engineering > Chemical and Process Engineering
    Depositing user: Pure Administrator
    Date deposited:04 May 2023 14:05
    Last modified:25 Apr 2024 01:33
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/85400
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