Rational Coordination Engineering of Fe–Co Dual-Atom Catalysts for Enhanced Oxygen Reduction Reaction via Synergistic Electronic Modulation
The development of efficient dual-atom catalysts (DACs) requires an atomic-level understanding on the microscopic coordination environment that is hard to characterize experimentally. Herein we rationally design DACs with diverse Fe-Co/N<sub>3</sub>O<sub>3</sub> configurations, among which the NN<sub>Fe</sub>OO<sub>Co</sub>NO-coordinated configuration is identified to exhibit superior stability and oxygen reduction reaction (ORR) catalytic activity based on first-principles calculations. Mechanistic analysis reveals that the ORR is triggered by side-on adsorption of O<sub>2</sub> on the Co site, enabled by strong hybridization between Co 3d<sub><i>xz/yz</i></sub> orbitals and O<sub>2</sub> π* antibonding states. The high-spin Fe<sup>2+</sup> acts as an electron reservoir by transferring charge to Co and lowering its d-band center. The Fe-Co synergy suppresses excessive *OH binding (Δ<i>G</i><sub>4</sub> = +0.107 eV in Fe-free Co@NO<sub>3</sub>) and positions the system to the ORR volcano apex. In summary, synergistic catalysis could be unlocked by rational coordination environmental design combined with spin-state-modulated charge redistribution.
Authors
- Huilong Dong (ORCID: https://orcid.org/0000-0002-4436-6392)
- Youyong Li (ORCID: https://orcid.org/0000-0002-5248-2756)
- Erjun Kan (ORCID: https://orcid.org/0000-0003-0433-4190)
- H.P. Wang (ORCID: https://orcid.org/0009-0000-3657-7168)
- Cheng Zhan (ORCID: https://orcid.org/0000-0002-4472-505X)
- Ming-Yuan Yu (ORCID: https://orcid.org/0009-0003-2935-3387)
Institutions
- Macau University of Science and Technology (MO)
- Suzhou University of Technology (CN)
- Suzhou University of Science and Technology (CN)
- Nanjing University of Science and Technology (CN)
- Soochow University (CN)
- Institute of Molecular Functional Materials (CN)
- Macao Polytechnic University (MO)
Publication Details
- Journal
- The Journal of Physical Chemistry Letters
- Published
- 2025-09-01
- DOI
- https://doi.org/10.1021/acs.jpclett.5c02229
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Fundo para o Desenvolvimento das Ciências e da Tecnologia
- Soochow University
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities