Correlation between the Molecular Properties of Semiconducting Polymers of Intrinsic Microporosity and Their Photocatalytic Hydrogen Production.

Increasing the interface area between organic semiconductor photocatalysts and electrolyte by fabricating nanoparticles has proven to be an effective strategy to increase photocatalytic hydrogen production activity. However, it remains unclear if increasing the interface by the introduction of porosity has as clear benefits for activity. To better inform future photocatalyst design, a series of polymers of intrinsic microporosity (PIMs) with the same conjugated backbone were synthesized as a platform to independently modulate the variables of porosity and relative hydrophilicity through the use of hydrophilic alcohol moieties protected by silyl ether protecting groups. When tested in the presence of ascorbic acid and photodeposited Pt, a strong correlation between the porosity and photocatalytic activity was found, with the more wettable analogue of two polymers of almost the same surface area delivering 7.3 times greater activity, while controlling for other variables. Transient absorption spectroscopic (TAS) investigation showed efficient intrinsic charge generation within 10 ps in two of the porous polymers, even without the presence of ascorbic acid or Pt. Detectable hole polarons were found to be immediately extracted by added ascorbic acid, suggesting the generation of reactive charges at regions readily accessible to electrolyte in the porous structures. This study directs organic semiconductor photocatalysts design toward more hydrophilic functionality for addressing exciton and charge recombination bottlenecks and clearly demonstrates the advantages of wettable porosity as a design principle.