摘要
Photoactive conjugated microporous polymers (CMPs) are emerging as porous materials capable of mediating the photocatalytic evolution of H 2 from water. In this study, we synthesized three pyrene-based CMPs (Py-F-CMP, Py-TPA-CMP, Py-TPE-CMP) through Sonogashira-Hagihara cross-couplings of 1,3,6,8-tetraethynylpyrene (Py-T, as a common monomer building block) with 2,7-dibromo-9H-fluorene (F-Br 2 ), tris(4-bromophenyl)amine (TPA-Br 3 ), and 1,1,2,2-tetrakis(4-bromophenyl)ethene (TPE-Br 4 ), respectively, in the presence of Pd(PPh 3 ) 4 in DMF/Et 3 N. We then characterized the chemical structures, crystallinities, thermal stabilities, surface morphologies, and porosities of these three new CMPs. Brunauer-Emmett-Teller (BET) analyses and tests of photocatalytic H 2 production revealed that Py-TPA-CMP displayed the highest BET surface area (454 m 2 g −1 ), highest total pore volume (0.28 cm 3 g −1 ), highest H 2 evolution rate (19 200 μmol h −1 g −1 ), and highest apparent quantum yield (15.3%) when compared with those of Py-F-CMP, Py-TPE-CMP, and other organic porous materials.