Authors: Zongge Li, Wenjun Kang, Jingkai Lin, Rui Li, Konggang Qu, Suyuan Zeng, Lei Wang, Fanpeng Meng, Huayang Zhang, Haibo Li
Published: 2025-03-17
Source: Full article
AbstractThe oxygen electrocatalytic activity of transition metal catalysts can be tuned by tailoring their microstructure to optimize electronic configuration. Here, a one‐step Coordination‐Selective Synthesis strategy is developed to integrate Co single‐atom sites and Fe‐based nanoparticles within the same matrix, enabling long‐range electronic interactions that enhance Co‐N4 reactivity and improve oxygen reduction reaction performance. X‐ray absorption spectroscopy confirmed that remote Fe‐based nanoparticles modulate the electron distribution at Co‐N4 sites. Structural characterizations reveal that the optimal catalyst, Co50%Fe50%‐NC, contains metallic Fe, Fe3O4, and Fe4N species. Electrochemical measurements show that it achieves onset and half‐wave potentials of 0.984 and 0.927 V versus RHE, surpassing Co100%‐NC with only Co‐N4 sites. Additionally, it demonstrates efficient oxygen evolution reaction performance, achieving an overpotential of 298 mV at 20 mA cm−2, comparable to RuO2. Density functional theory calculations reveal that Fe4N optimizes O‐containing intermediate adsorption/desorption, lowering the theoretical overpotential. Zn‐air batteries assembled with Co50%Fe50%‐NC exhibited superior performance to Pt/C, highlighting its potential for bifunctional oxygen electrocatalysis. This study provides an approach for designing high‐performance catalysts by utilizing synergistic interactions between atomic and nanoscale metal species.