Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN4 Sites for Oxygen Reduction

FeN₄ moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton‐exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe?N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatment. Here, we elucidate the FeN₄ site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF‐8‐derived nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe?N bond formation from complex carbonization and nitrogen doping, which correlates Fe?N bond properties with the activity and stability of FeN₄ sites as a function of the thermal activation temperature.