Modulating the Iron Microenvironment for a Cooperative Interplay Between Fe‐N‐C Single Atoms and Fe <sub>3</sub> C Nanoclusters on the Oxygen Reduction Reaction
The coexistence of single atoms and nanoparticles is shown to increase the oxygen reduction performance in Fe-N-C electrocatalysts, but the mechanisms underlying this synergistic effect remain elusive. In this study, model Fe-N-C electrocatalysts with controlled ratios of FeN<sub>4</sub> sites and Fe<sub>3</sub>C nanoclusters is systematically designed and synthesized. Experiments and density functional theory (DFT) computations reveal that Fe<sub>3</sub>C nanoclusters near FeN<sub>4</sub> sites modulate the electron density of the Fe single-atom microenvironment through an electron withdrawing effect. This substantially alters the oxygen reduction reaction (ORR) mechanisms and boosts the catalytic performance of FeN<sub>4</sub> sites. This study provides fundamental insights into the dynamic catalytic impact of single atoms and nanoparticle coexistence in advanced Fe-N-C electrocatalysts for the ORR, paving the way for further refinement through various combinations.
Authors
- Javier Quílez‐Bermejo (ORCID: https://orcid.org/0000-0003-2808-1036)
- M.T. Izquierdo (ORCID: https://orcid.org/0000-0002-2408-2528)
- Vanessa Fierro (ORCID: https://orcid.org/0000-0001-7081-3697)
- Mélanie Emo (ORCID: https://orcid.org/0000-0003-3599-6824)
- Feina Xu (ORCID: https://orcid.org/0000-0002-5437-9410)
- Andrea Zitolo (ORCID: https://orcid.org/0000-0002-2187-6699)
- Michaël Badawi (ORCID: https://orcid.org/0000-0002-3504-4180)
- Alain Celzard (ORCID: https://orcid.org/0000-0003-0073-9545)
- Anthony Dessalle
- Jean Wilfried Hounfodji (ORCID: https://orcid.org/0000-0002-7138-9346)
Institutions
- Centre National de la Recherche Scientifique (FR)
- Institut Universitaire de France (FR)
- Synchrotron soleil (FR)
- Laboratoire de Chimie Moléculaire (FR)
- Laboratoire Énergies et Mécanique Théorique et Appliquée (FR)
- Instituto de Carboquímica (ES)
- Institut Jean Lamour (FR)
- Laboratoire Lorrain de Chimie Moléculaire (FR)
- Université de Lorraine (FR)
Publication Details
- Journal
- Small
- Published
- 2024-11-26
- DOI
- https://doi.org/10.1002/smll.202409474
- Citations
- 12
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 1.23
Funders
- Universidad de Alicante
- European Commission
- Agence Nationale de la Recherche
- Grand Équipement National De Calcul Intensif
- European Regional Development Fund