Perylene-Containing Conjugated Microporous Polymers for Photocatalytic Hydrogen Evolution

Three perylene-containing conjugated microporous polymers (PrCMPs) are synthesized via Suzuki-Miyaura cross-coupling reaction from perylene with four polymerizable functional groups and a range of different substituted benzene derivatives. The pore property and bandgap of the resulting PrCMPs can be tuned by changing the comonomer of benzene with different substituted groups and positions. The photocatalytic performances of the polymers are highly dependent on the surface area, geometry, and bandgap of the PrCMPs. It was found that the 1,2,4,5-linked polymer of PrCMP-3 shows the highest hydrogen evolution rate (HER) of 12.1 mu mol h(-1) under UV-vis light irradiation among the three polymers because of its high surface area, broad light absorption, and suitable bandgap. PrCMP-3 also exhibits good photocatalytic stability for prolonged hydrogen production reaction. This result demonstrates that the crucial role of the linkage geometry offers a general principle for the rational design of conjugated microporous polymer photocatalysts.