A novel ferrocene-containing porous organic polymer (FPOP) utilized as a promising candidate for storing carbon dioxide and hydrogen. Although FPOP possesses lower porosity than many porous polymers, the gas capacities are higher or comparable to them, thereby revealing that the incorporation of ferrocene units into the network is an effective strategy to enhance the affinity between the framework and gas.

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Herein, we present two novel ferrocene-containing porous organic polymers, FPOP-1 and FPOP-2, by the Heck reactions of 1,1’-divinylferrocene with two tetrahedral silicon-centered units, i.e., tetrakis(4-bromophenyl)silane and tetrakis(4’-bromo-[1,1’-biphenyl]-4-yl)silane. The resulting materials possess high thermal stability and moderate porosity with the Brunauer–Emmer–Teller (BET) surface areas of 499 m2 g−1 (FPOP-1) and 354 m2 g−1 (FPOP-2) and total pore volumes of 0.43 cm3 g−1 (FPOP-1) and 0.49 cm3 g−1 (FPOP-2). The porosity is comparable to previously reported ferrocene-containing porous polymers. These materials possess comparable CO2 capacities of 1.16 mmol g−1 (5.10 wt%) at 273 K and 1.0 bar, and 0.54 mmol g−1 (2.38 wt%) at 298 K and 1.0 bar (FPOP-1). The found capacities are comparable to, or higher than many porous polymers having similar or higher surface areas. They have high isosteric heats of up to 32.9 kJ mol−1, proving that the affinity between the polymer network and CO2 is high, which can be explained by the presence of ferrocene units in the porous networks. These results indicate that these materials can be promisingly utilized as candidates for the storage or capture of CO2. More ferrocene-containing porous polymers can be designed and synthesized by combining ferrocene units with various aromatic monomers under this strategy and their applications could be explored.