Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer

Ezhov, Roman; Maximova, Olga; Lyu, Xiang; Leshchev, Denis; Stavitski, Eli; Serov, Alexey; Pushkar, Yulia

doi:10.1021/acsaem.3c02522

Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer

Journal Article · Thu Dec 28 00:00:00 EST 2023 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.3c02522· OSTI ID:2282945

^[1]; ^[1]; ^[2]; ^[3]; Stavitski, Eli ^[3]; Serov, Alexey ^[2]; ^[1]

Purdue University, West Lafayette, IN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Scaling up clean-energy applications necessitates the development of platinum group metal (PGM)-free fuel cell electrocatalysts with high activity, stability, and low cost. Here, X-ray absorption (XAS) at the Fe K-edge and Fe K_β X-ray emission (XES) spectroscopies were used to study the electronic structure of Fe centers in highly active Fe–N–C oxygen reduction catalysts with significant commercial potential. X-ray absorption near-edge structure (XANES) analysis has shown that the majority (>95%) of Fe centers are in the Fe³⁺ oxidation state, while extended X-ray absorption fine structure (EXAFS) detected a mixture of single site Fe–N₄ centers (>95%) and centers with short (~2.5 Å) Fe–Fe interactions of Fe metal and/or Fe-carbide nanoparticles (<5%) featuring the Fe^o oxidation state. Surprisingly, addition of Nafion, the most widely used ionomer, resulted in pronounced changes in the XAS spectra, consistent with a strong catalyst–ionomer interaction where long Fe–Fe interactions at ~3.1 Å were shown to be a feature of Fe³⁺ ions bound with the Nafion. We conclude that exposure to Nafion during the device formulation has a different effect from the aggressive acid leaching typically used in the preparation of Fe–N–C catalysts. Furthermore, it was hypothesized that the polymer interacts with single sites’ Fe³⁺ centers, as well as with graphene layers protecting the Fe^o nanoparticles, and extracts some Fe ions into the Nafion matrix.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); 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)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725; SC0012704

OSTI ID:: 2282945

Alternate ID(s):: OSTI ID: 2310278

Report Number(s):: BNL--225307-2024-JAAM

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 2 Vol. 7; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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