Iron redox behavior and oxygen reduction activity of Fe-N-C electrocatalysts in different electrolytes

Wang, Xiaoping; Ferrandon, Magali; Park, Jae Hyung; Shen, Jing-Jing; Kropf, A. Jeremy; Zhang, Hanguang; Zelenay, Piotr; Myers, Deborah J.

doi:10.1016/j.electacta.2023.141934

Iron redox behavior and oxygen reduction activity of Fe-N-C electrocatalysts in different electrolytes

Journal Article · Mon Jan 23 00:00:00 EST 2023 · Electrochimica Acta

DOI:https://doi.org/10.1016/j.electacta.2023.141934· OSTI ID:1973819

Wang, Xiaoping ^[1]; Ferrandon, Magali ^[1]; Park, Jae Hyung ^[1]; Shen, Jing-Jing ^[2]; Kropf, A. Jeremy ^[1]; ^[3]; ^[3]; Myers, Deborah J. ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Harvard Univ., Cambridge, MA (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The iron redox behavior and oxygen reduction reaction (ORR) activity of Fe-N-C ORR electrocatalysts synthesized by a variety of techniques were investigated as a function of the identity of the electrolyte anion (bisulfate/sulfate or perchlorate) at a constant pH. In situ X-ray absorption spectroscopy data support the assignment of the redox peaks in the voltammograms to the Fe³⁺/Fe²⁺ redox couple. It was found that for a given Fe-N-C catalyst, there is a correlation between the Fe redox couple peak potential and the ORR activity in perchloric acid electrolyte, but not in sulfuric acid electrolyte. While a higher Fe redox couple potential (≥ 110 mV higher) was observed in perchloric acid electrolyte, a higher ORR activity was obtained in sulfuric acid electrolyte. Here, the higher ORR activity observed in sulfuric acid than perchloric acid was correlated with the higher peak current and larger faradaic charge for the Fe redox couple. A study of the Fe redox behavior using a cavity microelectrode, eliminating the impact of ionomer, showed that the interaction of H₂SO₄ with Fe-N-C is stronger than that of HClO₄ and that Fe redox in both electrolytes is a reversible surface electrochemical reaction.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

Grant/Contract Number:: 89233218CNA000001; AC02-06CH11357

OSTI ID:: 1973819

Alternate ID(s):: OSTI ID: 2305331
OSTI ID: 1923815

Report Number(s):: LA-UR--23-20990

Journal Information:: Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 443; ISSN 0013-4686

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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