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PreprintCC BYChemRxiv

Nitrogen basicity dictates Fe-N-C-catalyzed aerobic oxidation activity

  • Jesse J. Martinez1,2
  • Ian J. Garvey1,2
  • Woonjin Jang1,2
  • Patrick Q. Kelly1,2
  • Evelyn M. Widmaier1,2
  • Melissa N. Hall1,2
  • Jason S. Bates1,2
  • Shannon S. Stahl1,2
  1. 1Department of Chemistry
  2. 2University of Wisconsin–Madison
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Abstract

Iron-metalated nitrogen-doped carbon (Fe-N-C) materials rival platinum-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, and O2 reduction is proposed to occur at atomically dispersed Fe atoms coordinated by nitrogen within the graphitic material (FeNx). In recent years, similar catalysts have been shown to be effective for aerobic oxidation of organic substrates, often under non-aqueous conditions that are very different from electrocatalytic ORR conditions. Such reactions have been the focus of limited mechanistic attention, and little is known about the active sites and/or catalyst features that contribute to improved activity. Here, we investigate Fe-NC-catalyzed aerobic oxidation of hydroquinone to benzoquinone and two other organic reactions. The FeNx site density is found to have little influence over catalytic activity. Instead, we find that the basicity of nitrogen atoms in the Fe-N-C surface is the dominant feature that correlates with catalytic activity, with diagnostic insights gained from binding isotherm measurements with pivalic acid. Fe-N-C catalytic activity is shown to correlate directly with the pivalic acid binding constant (Kads) across a series of different catalysts. These insights provide a valuable foundation for future development and optimization of improved aerobic oxidation catalysts.

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Cite

BibTeXRIS
BibTeX
@misc{martinez2026nitrogen,
  title = {{Nitrogen basicity dictates Fe-N-C-catalyzed aerobic oxidation activity}},
  author = {Jesse J. Martinez and Ian J. Garvey and Woonjin Jang and Patrick Q. Kelly and Evelyn M. Widmaier and Melissa N. Hall and Jason S. Bates and Shannon S. Stahl},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009581/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009581/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Nitrogen basicity dictates Fe-N-C-catalyzed aerobic oxidation activity
AU  - Jesse J. Martinez
AU  - Ian J. Garvey
AU  - Woonjin Jang
AU  - Patrick Q. Kelly
AU  - Evelyn M. Widmaier
AU  - Melissa N. Hall
AU  - Jason S. Bates
AU  - Shannon S. Stahl
PY  - 2026
DA  - 2026/09/28
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009581/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009581/v1
AB  - Iron-metalated nitrogen-doped carbon (Fe-N-C) materials rival platinum-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, and O2 reduction is proposed to occur at atomically dispersed Fe atoms coordinated by nitrogen within the graphitic material (FeNx). In recent years, similar catalysts have been shown to be effective for aerobic oxidation of organic substrates, often under non-aqueous conditions that are very different from electrocatalytic ORR conditions. Such reactions have been the focus of limited mechanistic attention, and little is known about the active sites and/or catalyst features that contribute to improved activity. Here, we investigate Fe-NC-catalyzed aerobic oxidation of hydroquinone to benzoquinone and two other organic reactions. The FeNx site density is found to have little influence over catalytic activity. Instead, we find that the basicity of nitrogen atoms in the Fe-N-C surface is the dominant feature that correlates with catalytic activity, with diagnostic insights gained from binding isotherm measurements with pivalic acid. Fe-N-C catalytic activity is shown to correlate directly with the pivalic acid binding constant (Kads) across a series of different catalysts. These insights provide a valuable foundation for future development and optimization of improved aerobic oxidation catalysts.
ER  -