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Abstract Porous functional organic polymers have attracted significant interest due to their diverse applications in adsorption/separation, electrocatalysis, photocatalysis, photosensing, and electronics. In these applications, performance depends on interactions between guest molecules and polymer frameworks. Consequently, the introduction of mesopores (2–50 nm) and macropores (50–300 nm) can significantly enhance functionality by simultaneously increasing the exposed active surface area and facilitating molecular diffusion within the polymer matrix. However, a wide range of porous polymers achievable through previous approaches, including surfactant and polystyrene templating, has been severely limited to a few less functional polymers due to the typically aqueous environment used during templating reaction and the need for template removal after polymerization. In this work, a universal approach is demonstrated that utilizes water‐soluble templates to synthesize functional meso‐ and macro‐porous organic polymers via solid‐state polymerization of aldehydes and amines (Schiff reaction), using perovskite metal fluorides (K M F 3 ) as sacrificial templates. By precisely tuning the particle sizes of metal fluoride templates, accurate control over pore sizes across the mesoscopic and macroscopic scales is achieved. A variety of aldehyde‐amine combinations yield semiconductive meso‐ and macro‐porous organic polymers. This versatile synthetic strategy is broadly applicable to a wide range of polymer systems, enabling simultaneous enhancement of surface area and molecular diffusion, thereby optimizing functional performance.
Asakura et al. (Tue,) studied this question.