Spectroscopic insights into the nature of active sites in iron-nitrogen-carbon electrocatalysts for oxygen reduction in acid

Qingying Jia, Nagappan Ramaswamy, Urszula Tylus, Kara Strickland, Jingkun Li, Alexey Serov, Kateryna Artyushkova, Plamen Atanassov, Jacob Anibal, Cenk Gumeci, Scott Calabrese Barton, Moulay Tahar Sougrati, Frederic Jaouen, Barr Halevi, Sanjeev Mukerjee

    Research output: Research - peer-reviewArticle

    • 21 Citations

    Abstract

    Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal-air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via different methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N-C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe-N4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe-N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.

    LanguageEnglish (US)
    JournalNano Energy
    DOIs
    StateAccepted/In press - Feb 17 2016

    Profile

    Electrocatalysts
    Nitrogen
    Carbon
    Iron
    Oxygen
    Catalysts
    Acids
    Fuel cells
    Metals
    Durability
    Oxidation-Reduction
    Catalyst supports
    Hydrogen Peroxide
    Electrolytes
    Catalysis
    Free Radicals
    Surface properties
    Catalyst activity
    Polymers
    Thermodynamic properties

    Keywords

    • Active site
    • In situ XAS, redox catalysis
    • Non-platinum group catalyst
    • Oxygen reduction

    ASJC Scopus subject areas

    • Renewable Energy, Sustainability and the Environment
    • Materials Science(all)
    • Electrical and Electronic Engineering

    Cite this

    Spectroscopic insights into the nature of active sites in iron-nitrogen-carbon electrocatalysts for oxygen reduction in acid. / Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula; Strickland, Kara; Li, Jingkun; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen; Anibal, Jacob; Gumeci, Cenk; Barton, Scott Calabrese; Sougrati, Moulay Tahar; Jaouen, Frederic; Halevi, Barr; Mukerjee, Sanjeev.

    In: Nano Energy, 17.02.2016.

    Research output: Research - peer-reviewArticle

    Jia, Q, Ramaswamy, N, Tylus, U, Strickland, K, Li, J, Serov, A, Artyushkova, K, Atanassov, P, Anibal, J, Gumeci, C, Barton, SC, Sougrati, MT, Jaouen, F, Halevi, B & Mukerjee, S 2016, 'Spectroscopic insights into the nature of active sites in iron-nitrogen-carbon electrocatalysts for oxygen reduction in acid' Nano Energy. DOI: 10.1016/j.nanoen.2016.03.025
    Jia, Qingying ; Ramaswamy, Nagappan ; Tylus, Urszula ; Strickland, Kara ; Li, Jingkun ; Serov, Alexey ; Artyushkova, Kateryna ; Atanassov, Plamen ; Anibal, Jacob ; Gumeci, Cenk ; Barton, Scott Calabrese ; Sougrati, Moulay Tahar ; Jaouen, Frederic ; Halevi, Barr ; Mukerjee, Sanjeev. / Spectroscopic insights into the nature of active sites in iron-nitrogen-carbon electrocatalysts for oxygen reduction in acid. In: Nano Energy. 2016
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