The chemical state of iron species influence on the performance of Fe–N–C bifunctional electrocatalyst for Zn–air batteries

Abstract Fe–N–C materials have emerged as promising alternatives to precious metals for oxygen reduction reaction/oxygen evolution reaction (ORR/OER). In this study, a strategy is presented to investigate the influence of different chemical states of iron species in Fe–N–C materials on their electrocatalytic performance. Three Fe–N–C catalysts, containing either zero-valent Fe or Fe 3 O 4 nanoparticles, are synthesized using acid pickling, high-speed centrifugation and ultrasound-assisted hydrothermal methods, respectively. The findings manifest that the chemical state of iron significantly affects the electrocatalytic activity of Fe–N X active sites, namely zero-valent Fe enhancing Fe–N X activity while Fe 3 O 4 weakening its activity. Notably, the Fe@FeNC catalyst containing only zero-valent iron, demonstrates the only 0.621 V potential difference between the ORR half-wave potential and the OER potential at 10 mA cm −2 . Furthermore, the rechargeable Zn–air battery assembled with Fe@FeNC as the air cathode exhibits a remarkable peak power density of 179.0 mW cm −2 , excellent cycling stability over 210 h (with a cycle frequency of one every 10 min), and the minimal voltage gap of 0.710 V. These results reveal the significance of different chemical states of metal-based nanoparticles in Fe–N X activity of Fe–N–C catalysts and offer insights into the rational design of electrocatalysts with exceptional activity and versatile applications.