Bio-Inspired Hierarchical Nanoreactor With Hetero-Coordinated Fe-P-Co Bridges for Whole-Pathway-Regulated Electrocatalytic Oxygen Reduction

[EN] Efficient oxygen reduction reaction (ORR) requires coordination of oxygen adsorption, transport, and catalysis at active sites. Yet most studies address only one step, overlooking whole-pathway O2 regulation and thus limiting performance. Here, we report a bioinspired Co-doped Fe2P on N-doped c...

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Detalles Bibliográficos
Autores: Xu, Qiaoling, Zhang, Lei, Li, Xiayu, Xu, Weihang, Ren, Linyi, Xu, Mai, Zhou, Yingtang, García Gómez, Hermenegildo|||0000-0002-9664-493X
Tipo de recurso: artículo
Fecha de publicación:2026
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:dnet:riunet______::e40019d462ed20cf99244c6955067dd6
Acceso en línea:https://riunet.upv.es/handle/10251/233499
Access Level:acceso abierto
Palabra clave:Co-Fe electronic synergy
ORR performance
Eucalyptus-like nanotube
Hetero-coordinated Fe P Co bridges
Oxygen adsorption and transport dynamics
Descripción
Sumario:[EN] Efficient oxygen reduction reaction (ORR) requires coordination of oxygen adsorption, transport, and catalysis at active sites. Yet most studies address only one step, overlooking whole-pathway O2 regulation and thus limiting performance. Here, we report a bioinspired Co-doped Fe2P on N-doped carbon featuring a hierarchical eucalyptus-like nanoarchitecture, engineered to regulate oxygen throughout the electrochemical cycle, where Fe-P-Co hetero-coordinated bridges anchored to the carbon substrate through Fe & horbar;N bonds induce strong electronic coupling and polarization. The hierarchical structure generated local electric fields that enriched OH- and O2, while multilevel porosity accelerated oxygen transport. This enabled coordinated optimization of oxygen adsorption, transfer, and active-site electronic configuration. This nanohybrid achieved a half-wave potential of 0.938 V vs. RHE, sustained discharge in Al-air batteries for 373 h, and delivered an energy density of 3487 Wh/kg. Theoretical simulations revealed that Co-doping shortened Fe & horbar;P bonds and tuned the Fe electronic environment, lowering the d-band center and weakening Fe 3d-O 2p interactions, which reduced the *OH desorption barrier and accelerated ORR kinetics. In situ Raman spectroscopy revealed that Fe-P-Co bridges served as active centers facilitating *OH release during ORR. These findings indicate that integrating hierarchical architecture, hetero-coordinated Fe-P-Co bridges, and electronic-state modulation enables whole-pathway O2 management for efficient oxygen electrocatalysis.