Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Bates, Jason S.; Martinez, Jesse J.; Hall, Melissa N.; Al-Omari, Abdulhadi A.; Murphy, Eamonn; Zeng, Yachao; Luo, Fang; Primbs, Mathias; Menga, Davide; Bibent, Nicolas; Sougrati, Moulay Tahar; Wagner, Friedrich E.; Atanassov, Plamen; Wu, Gang; Strasser, Peter; Fellinger, Tim-Patrick; Jaouen, Frédéric; Root, Thatcher W.; Stahl, Shannon S.

doi:10.1021/jacs.3c08790

Title: Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Journal Article · 19 November 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c08790 · OSTI ID:2274937

^[1]; Martinez, Jesse J. ^[2];

^[2]; Al-Omari, Abdulhadi A. ^[2];

^[3]; Zeng, Yachao ^[4];

^[5];

^[5]; Menga, Davide ^[6];

^[7];

^[7]; Wagner, Friedrich E. ^[6];

^[3];

^[4];

^[5];

^[8];

^[7];

^[2];

^[2]

University of Wisconsin - Madison, WI (United States); University of Wisconsin - Madison
University of Wisconsin - Madison, WI (United States)
University of California, Irvine, CA (United States)
University at Buffalo, The State University of New York, NY (United States)
Technical University Berlin (Germany)
Technische Universität München (TUM), Garching (Germany)
Univ. Montpellier (France)
Bundesanstalt für Materialforschung und -prüfung (BAM), Berlin (Germany)

Mononuclear Fe ions ligated by nitrogen (FeN_x) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O₂ reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN_x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN_x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO₂^– on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN_x sites or the coexistence of aggregated Fe species in addition to FeN_x. The FeN_x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

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Research Organization:: University of Wisconsin - Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 2274937

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

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