@article{Liu2025, 
author = {Jiayi Liu and Jingwen Yin and Yingzi Lin and Mingxin Pang and Huan Pang and Songtao Zhang and Lin Xu and Jun Yang and Yawen Tang},
title = {Engineering of Fe d-band center in Fe3O4/CeO2 hetero-nanoparticles via orbital coupling for high-efficiency oxygen reduction electrocatalysis},
year = {2025},
journal = {Nano Research},
volume = {18},
number = {1},
pages = {94907016},
keywords = {oxygen reduction reaction, electrospinning, hetero-nanoparticles, interfacial engineering, orbital coupling},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907016},
doi = {10.26599/NR.2025.94907016},
abstract = {The deliberate engineering of the d-band center of metal site represents an effective strategy to boost the intrinsic electrocatalytic performance toward the oxygen reduction reaction (ORR). Herein, following a heterointerface-induced orbital coupling rationale, we report a judicious design of an efficient ORR electrocatalyst consisting of Fe3O4/CeO2 hetero-nanoparticles in-situ encased into N-doped carbon nanofibers (abbreviated as Fe3O4/CeO2@N-CNFs hereafter). The theoretic calculations uncover that the Fe3O4/CeO2 heterointerface-triggered orbital coupling can cause the down shift of the d-band center positions of Fe sites, which leads to the weakened chemisorption of oxygenated groups and lowered energy barrier for the potential-determining step, ultimately dramatically boosting the ORR intrinsic activity. As a consequence, the well-designed Fe3O4/CeO2@N-CNFs display admirable ORR activity with a half-wave potential of 0.84 V and outstanding structural/electrochemical stability in an alkaline electrolyte, surpassing the commercial Pt/C benchmark and a majority of recently reported Fe3O4-based electrocatalysts. More encouragingly, the Fe3O4/CeO2@N-CNFs-incorporated Zn-air battery outperforms the Pt/C-assembled counterpart with higher power density, larger energy density, and excellent cycling stability, serving as a competent candidate for ORR-involved renewable energy setups. This study offers an innovative approach for the rational manipulation of the d-band center and interfacial electron behavior of active sites toward the optimization of electrocatalytic performance.}
}