Molecular Expansion for Constructing Porous Organic Polymers with High Surface Areas and Well-Defined Nanopores

Construction of porous organic polymers (POPs) with high surface areas, well-defined nanopores, and excellent stability remains extremely challenging because of the unmanageable reaction process. Until now, only a few reported POPs have Brunauer-Emmett-Teller (BET) surface areas (S_BET ) exceeding 3000 m²  g^-1 . Herein, we demonstrate a molecular expansion strategy to integrate high surface areas, large nanopore sizes, and outstanding stability into POPs. A series of hyper-crosslinked conjugated polymers (HCCPs) with exceptional porosity are synthesized through this strategy. Specially, HCCP-6 and HCCP-11 exhibit the highest surface areas (S_BET >3000 m²  g^-1 ) and excellent total pore volumes (up to 3.98 cm³  g^-1 ) among these HCCPs. They present decent total CH₄ storage capacities of 491 and 421 mg g^-1 at 80 bar and 298 K, respectively. Meanwhile, they are highly stable in harsh environments. The facile and general molecular expansion strategy would lead to improved synthetic routes of POPs for desired functions.