A novel dianhydride 3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl

biphenyl dianhydride (BPEBPDA) and a new tetramine monomer 5,10,15,20-

tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) were successfully

synthesized. Porphyrin-based polyimides (PPBPIs) were synthesized from BPEBPDA

and porphyrin-based building blocks (TAPP and TAPEPP) via polymerization reactions. The porphyrin-based porous polyimide

networks (PPBPI-CRs) were obtained from PPBPIs through thermal crosslinking reactions. The PPBPI-CRs exhibited BET surface areas

(682 m2 g-1 and 693 m2 g-1) and CO2

uptakes

(2.0 mmol g-1 and 1.67 mmol g-1 at 273 K and 1 bar) as

well as the separation factors of CO2/N2

(37.63, 28.97) and CO2/CH4 (7.51, 5.61).

Meanwhile, PPBPI-CRs showed an enhanced CO2 isosteric enthalpies of adsorption (25.1 kJ mol-1 and

30.1 kJ mol-1) than other porous polymers.