Non‐Precious Metal‐Doped Carbon Materials Derived From Porphyrin‐Based Porous Organic Polymers for Oxygen Reduction Electrocatalysis

The cathodic oxygen reduction reaction (ORR) is important in the development of renewable energy devices, to produce novel and non-precious metal catalysts with high electrocatalytic activity to reduce the consumption of non-renewable platinum (Pt) catalyst. In this work, we developed N-doped and Fe/N dual-doped porous carbons as catalysts for ORR simply by high-temperature pyrolysis of porphyrin-based conjugated microporous polymers (CMPs). By combination of heteroatom doping, highly porous structure and tubular morphology, the as-prepared carbon samples exhibited high electrocatalytic activity with 4-electron transfer mechanism, nearly close to the commercial Pt/C catalyst. In particular, among these samples, the Fe/N-CMP-1000 displayed a higher onset potential (0.95 eV), positive half-wave potential (0.85 eV) and limiting current density value (5.1 mA cm-2 ) as well as good durability and better methanol tolerance contrasting with Pt/C catalyst, suggesting that the as-prepared metal-free catalysts from porphyrin-based CMPs show great potential for ORR.