{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Cheng R"],"funding":["National Natural Science Foundation of China"],"pagination":["e14432"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12822467"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["13(4)"],"pubmed_abstract":["The oxygen reduction reaction (ORR) remains a major obstacle in green electrochemical energy conversion, driving the pursuit of cost-effective noble-metal-free catalysts. Transition metal (TM) and rare-earth (RE) compounds have emerged as promising alternatives. However, their catalytic activity is hindered by sluggish electron transfer and restrictive scaling relationships. Herein, a TM/RE heterostructural catalyst that integrates the complementary features of Fe<sub>3</sub>N's tunable 3d orbitals and spin polarization with CeO<sub>2</sub>'s partially filled 4f orbitals and facile Ce<sup>4+</sup>/Ce<sup>3+</sup> redox transitions, enabling dual-phase catalytic participation, is designed. The Fe<sub>3</sub>N/CeO<sub>2</sub> heterostructure forms a dual-site catalytic heterointerface, which promotes charge redistribution and optimizes intermediate adsorption. This synergy originates from the 4f-3d orbital ladder via Ce─O─Fe coordination, enabling directed electron transfer, Fermi level equilibration, and increased carrier density. The interfacial coupling further modulates the Fe spin state, enhances Ce─O covalency, and enriches unpaired electrons, thereby co-activating both phases and establishing a cascade pathway at the heterointerface that circumvents conventional scaling constraints. The proposed mechanism is further verified by in situ Raman spectroscopy and theoretical calculations. The Fe<sub>3</sub>N/CeO<sub>2</sub> achieves a half-wave potential of 0.874 V and delivers a maximum power density of 157.8 mW cm<sup>-2</sup> in aluminum-air batteries, outperforming commercial Pt/C and underscoring the application prospects of RE-based heterostructures for next-generation energy technologies."],"journal":["Advanced science (Weinheim, Baden-Wurttemberg, Germany)"],"pubmed_title":["Activation of Cascade Pathway for Oxygen Reduction via 4f-3d Orbital Ladder-Driven Dual-Site Synergy."],"pmcid":["PMC12822467"],"funding_grant_id":["52274302"],"pubmed_authors":["Li H","Fu C","Cheng R","He X","Han Y","Li K","Song J"],"additional_accession":[]},"is_claimable":false,"name":"Activation of Cascade Pathway for Oxygen Reduction via 4f-3d Orbital Ladder-Driven Dual-Site Synergy.","description":"The oxygen reduction reaction (ORR) remains a major obstacle in green electrochemical energy conversion, driving the pursuit of cost-effective noble-metal-free catalysts. Transition metal (TM) and rare-earth (RE) compounds have emerged as promising alternatives. However, their catalytic activity is hindered by sluggish electron transfer and restrictive scaling relationships. Herein, a TM/RE heterostructural catalyst that integrates the complementary features of Fe<sub>3</sub>N's tunable 3d orbitals and spin polarization with CeO<sub>2</sub>'s partially filled 4f orbitals and facile Ce<sup>4+</sup>/Ce<sup>3+</sup> redox transitions, enabling dual-phase catalytic participation, is designed. The Fe<sub>3</sub>N/CeO<sub>2</sub> heterostructure forms a dual-site catalytic heterointerface, which promotes charge redistribution and optimizes intermediate adsorption. This synergy originates from the 4f-3d orbital ladder via Ce─O─Fe coordination, enabling directed electron transfer, Fermi level equilibration, and increased carrier density. The interfacial coupling further modulates the Fe spin state, enhances Ce─O covalency, and enriches unpaired electrons, thereby co-activating both phases and establishing a cascade pathway at the heterointerface that circumvents conventional scaling constraints. The proposed mechanism is further verified by in situ Raman spectroscopy and theoretical calculations. The Fe<sub>3</sub>N/CeO<sub>2</sub> achieves a half-wave potential of 0.874 V and delivers a maximum power density of 157.8 mW cm<sup>-2</sup> in aluminum-air batteries, outperforming commercial Pt/C and underscoring the application prospects of RE-based heterostructures for next-generation energy technologies.","dates":{"release":"2026-01-01T00:00:00Z","publication":"2026 Jan","modification":"2026-06-14T05:04:36.076Z","creation":"2026-06-14T03:08:32.543Z"},"accession":"S-EPMC12822467","cross_references":{"pubmed":["41164918"],"doi":["10.1002/advs.202514432"]}}