An Interpenetrating Porous Organic Polymer as a Precursor for FeP/Fe2P‐Embedded Porous Carbon toward a pH‐Universal ORR Catalyst

Abstract Interpenetrating porous organic polymers (PNFc‐POP) inspired by the structure of DNA were synthesized through a two‐stage polymerization method under catalyst‐free conditions. A ferrocene‐rich hyper‐crosslinked polymer (Fc‐melamine) was interwoven with cyclotriphosphazene‐based conjugated porous polymer (PN‐CMP) to obtain an interconnected polymer network (PNFc‐POP). The sequential interpenetrating polymer network contained a diverse range of heteroatoms (P, N, O and Fe) and exhibited a large BET surface area. Simple pyrolysis of the dual polymer interweaved skeletons at 900 °C afforded nanocrystalline FeP/Fe 2 P‐embedded N and P codoped porous carbon composites. The optimal catalyst obtained by the pyrolysis of PNFc‐POP at 900 °C (PNFc‐900) exhibited hierarchical porosity and large BET surface areas. It also exhibited excellent oxygen reduction reaction catalytic activities over the entire pH range. The onset potential ( E onset =1.01 V) and half‐wave potential ( E 1/2 =0.86 V) of PNFc‐900 exceeded those of commercial Pt/C ( E onset =0.99 V and E 1/2 =0.84 V) in alkaline conditions. The obtained catalysts with a four‐electron transfer pathway for the reduction of oxygen also displayed excellent long‐term stability and methanol tolerance.