Single-atom Fe catalysts with pyrrolic-type FeN4 sites for efficient oxygen reduction reaction: Identifying the roles of different N species

Developing electrocatalysts with efficient cathode oxygen reduction reaction (ORR), for example, iron-based single-atom catalysts (Fe-SACs), has been deemed necessary to accelerate the commercialisation process of zinc (Zn)–air batteries. Nevertheless, determining how various nitrogen species and active metal centres coordinate on an atomic scale remains unclear and inadequately explained. Herein, we demonstrate a soft-template-aided technique using Fe-containing molecules (e.g. iron phthalocyanine [FePc], Fe-1,10-phenanthroline [Fe-Phen] and Fe-glucose) to enhance the performance of Fe-SACs in terms of ORR. In this technique, FePc molecules can be converted into atomically dispersed pyrrolic-type iron–nitrogen (FeN4) sites during a pyrolytic process. The resultant catalyst exhibits excellent ORR activity (half-wave potential = 0.90 V) in alkaline medium and standing battery performance when used in Zn–air batteries (peak power density = 197.3 mW cm−2 and specific capacity = 796.2 mAh g−1). As per the findings from control experiments and characterisation studies, electron transfer between the support and the active Fe centre amplifies the ORR performance. Theoretical calculations substantiate that Fe sites coordinated with pyrrolic N atoms govern the electronic configuration of the catalysis, reducing the free energy absorption of reaction intermediates and thus increasing its intrinsic ORR capability. Herein, we aim to offer a fresh perspective on the relation between coordination environments and catalytic activity in ORR catalysts.