Evidence for the stabilization of FeN<sub>4</sub> sites by Pt particles during acidic oxygen reduction.

Ishiki, Nicolas A; Teixeira Santos, Keyla; Bibent, Nicolas; Kumar, Kavita; Reichmann, Ina; Ku, Yu-Ping; Asset, Tristan; Dubau, Laetitia et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

While Fe-N-C materials have shown promising initial oxygen reduction reaction (ORR) activity, they lack durability in acidic medium. Key degradation mechanisms include FeN<sub>4</sub> site demetallation and deactivation by reactive oxygen species. Here we show for mainstream Fe-N-Cs that adding 1 wt.% Pt nanoparticles via a soft polyol method results in well-defined and stable Pt/Fe-N-C hybrids. The Pt addition strongly reduces the H<sub>2</sub>O<sub>2</sub> production and Fe leaching rate during ORR, while post mortem Mössbauer spectroscopy reveals that the highly active but unstable Fe(III)N<sub>4</sub> site is partially stabilized. The similar H<sub>2</sub>O<sub>2</sub> electroreduction activity of Pt/Fe-N-C and Fe-N-C and other analyses point toward a long-distance electronic effect of Pt nanoparticles in stabilizing FeN<sub>4</sub> sites. Computational chemistry reveals that spin polarization of distant Pt atoms mitigates the structural changes of FeN<sub>4</sub> sites upon adsorption of oxygenated species atop Fe, especially in high-spin state.