Self‐Sacrificial Template Synthesis of Fe‐N‐C Catalysts with Dense Active Sites Deposited on A Porous Carbon Network for High Performance in PEMFC

Iron‐nitrogen‐carbon (Fe‐N‐C) single‐atom catalysts are promising sustainable alternatives to the costly and scarce platinum (Pt) to catalyze the oxygen reduction reactions (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). However, Fe‐N‐C cathodes for PEMFC are made thicker than Pt/C ones, in order to compensate for the lower intrinsic ORR activity and site density of Fe‐N‐C materials. The thick electrodes are bound with mass transport issues that limit their performance at high current densities, especially in H2/air PEMFCs. Practical Fe‐N‐C electrodes must combine high intrinsic ORR activity, high site density, and fast mass transport. Herein, it has achieved an improved combination of these properties with a Fe‐N‐C catalyst prepared via a two‐step synthesis approach, constructing first a porous zinc‐nitrogen‐carbon (Zn‐N‐C) substrate, followed by transmetallating Zn by Fe via chemical vapor deposition. A cathode comprising this Fe‐N‐C catalyst has exhibited a maximum power density of 0.53 W cm−2 in H2/air PEMFC at 80 °C. The improved power density is associated with the hierarchical porosity of the Zn‐N‐C substrate of this work, which is achieved by epitaxial growth of ZIF‐8 onto g‐C3N4, leading to a micro‐mesoporous substrate. A Fe‐N‐C catalyst with a porous network structure integrated with high active site density is constructed via iron deposition on a porous Zn‐N‐C substrate. The Zn‐N‐C substrate derived from the epitaxial growth of ZIF‐8s onto g‐C3N4 consequently imparts excellent mass transport through the resulting Fe‐N‐C catalyst layer. A cathode comprising this Fe‐N‐C catalyst has exhibited a maximum power density of 0.53 W cm‐2 in H2/air PEMFC at 80 °C.