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Cyclotriphosphazene (CP) based porous organic polymers (POPs) have been designed and prepared. The introduction of CP into the porous skeleton endowed special thermal stability and outstanding flame retardancy to prepared polymers. The nonflammable level of PNK‐CMP fabricated via the condensation of 2,2′‐(1,4‐phenylene)diacetonitrile (DAN) and hexakis(4‐acetylphenoxy)cyclotriphosphazene (HACTP) through Knoevenagel reaction, in vertical burning tests reached V‐2 class (UL‐94) and the limiting oxygen index (LOI) reached 20.8 %. When used as additive, PNK‐CMP could suppress the dissolving out of PEPA effectively, reducing environment pollution and improving the flame retardant efficiency. The POP and PEPA co‐added PU (m POP %: m PEPA %=5.0 %: 5.0 %) could not be ignited under simulated real‐scale fire conditions. The nonflammable level of POP/PEPA/PU in vertical burning tests (UL‐94) reached V‐0 class with a LOI as high as 23.2 %. The smoke emission could also be suppressed, thus reducing the potential for flame spread and fire hazards. Furthermore, carbonization of PNK‐CMP under the activation of KOH yield a hyperporous carbon (PNKA‐800) with ultrahigh BET surface area (3001 m 2  g −1 ) and ultramicropore size showing excellent ORR activity in alkaline conditions.

Porous Organic Polymers as Fire‐Resistant Additives and Precursors for Hyperporous Carbon towards Oxygen Reduction Reactions