The Polymer Society of Korea

Abstract

The incorporation of spiro units into conjugated polymer backbones disrupts dense packing, creating permanent porosity that improves dispersion in aqueous media and facilitates water uptake without compromising backbone planarity. These features promote efficient charge separation and enhance photocatalytic hydrogen evolution. In this study, spiro-containing polymers were synthesized by integrating spiro moieties into a dibenzo[b,d]thiophene sulfone-based backbone. To explore electronic effects, both electron-donating and electron-withdrawing substituents were introduced onto the spiro unit. All polymers showed improved hydrogen evolution rates (HER), with the electron-withdrawing group exhibiting the highest activity due to enhanced electron extraction. These results demonstrate the synergistic role of spiro-induced porosity and tunable electronic properties in boosting the photocatalytic efficiency of conjugated polymers for solar-driven hydrogen production.