Novel CdFe Bimetallic Complex-Derived Ultrasmall Fe- and N-Codoped Carbon as a Highly Efficient Oxygen Reduction Catalyst

During the development of oxygen reduction reaction electrocatalysts, transition-metal nanoparticles embedded in N-doped graphene have attracted increasing attention owing to their low-priced, minimal environmental impact, and satisfying performance. In this study, a new organic-cadmium (Cd) complex formed through Cd2+ coordination with p-phenylenediamine (PPD) was used to synthesize highly active Fe-embedded N-doped carbon catalysts for the first time. It is significant that with the decreasing molar ratio of Cd/Fe, an obvious microstructure evolution was observed in Cd–Fe–PPD from diamond-like blocks to thick flakes, and further bloomed into flowerlike shapes with ultrathin petals and then eventually exhibited large block starfish-like shapes. After carbonization, Cd was removed, slack and porous N-doped carbon was formed, and Fe was assembled in the N-doped carbon. Similar phenomenon was also observed in Co–PPD. The optimized Fe/NPC-2 material featuring uniform and well-dispersed 3–5 nm Fe nanoparticles embedded in two-dimensional ultrathin carbon nanosheets delivered excellent electrocatalytic performance (Eonset: 0.96 V vs reversible hydrogen electrode (RHE), E1/2: 0.84 V vs RHE), which is very close to those of commercial platinum on carbon (Pt/C) (Eonset: 0.95 V vs RHE, E1/2: 0.84 V vs RHE), and its methanol tolerance and durability also surpass those of Pt/C.