Hierarchically Porous M–N–C (M = Co and Fe) Single‐Atom Electrocatalysts with Robust MNx Active Moieties Enable Enhanced ORR Performance

The great interest in fuel cells inspires a substantial amount of research on nonprecious metal catalysts as alternatives to Pt‐based oxygen reduction reaction (ORR) electrocatalysts. In this work, bimodal template‐based synthesis strategies are proposed for the scalable preparation of hierarchically porous M–N–C (M = Fe or Co) single‐atom electrocatalysts featured with active and robust MN2 active moieties. Multiscale tuning of M–N–C catalysts regarding increasing the number of active sites and boosting the intrinsic activity of each active site is realized simultaneously at a single‐atom scale. In addition to the antipoisoning power and high affinity for O2, the optimized Fe–N–C catalysts with FeN2 active site presents a superior electrocatalytic activity for ORR with a half‐wave potential of 0.927 V (vs reversible hydrogen electrode (RHE)) in an alkaline medium, which is 49 and 55 mV higher than those of the Co–N–C counterpart and commercial Pt/C, respectively. Density functional theory calculations reveal that the FeN2 site is more active than the CoN2 site for ORR due to the lower energy barriers of the intermediates and products involved. The present work may help rational design of more robust ORR electrocatalysts at the atomic level, realizing the significant advances in electrochemical conversion and storage devices. Up‐scalable synthesis of hierarchically porous Fe–N–C single‐atom electrocatalysts with robust FeN2 active moieties is demonstrated. The obtained Fe–N–C catalysts exhibit superior electrocatalytic activity for oxygen reduction reaction with a half‐wave potential of 0.927 V, which is 49 and 55 mV higher than those of the Co–N–C counterpart and commercial Pt/C, respectively.