Triazine and Fused Thiophene-Based Donor-Acceptor Type Semiconducting Conjugated Polymer for Enhanced Visible-Light-Induced H2 Production

Conjugated polymers have attracted significant attention in the field of photocatalysis due to their exceptional properties, including versatile optimization, cost-effectiveness, and structure stability. Herein, two conjugated porous polymers, PhIN-CPP and ThIN-CPP, based on triazines, were meticulously designed and successfully synthesized using benzene and thiophene as building blocks. Based on UV diffuse reflection spectra, the photonic band gaps of PhIN-CPP and ThIN-CPP were calculated as 2.05 eV and 1.79 eV. The PhIN-CPP exhibited a high hydrogen evolution rate (HER) of 5359.92 μmol·g−1·h−1, which is 10 times higher than that of Thin-CPP (538.49 μmol·g−1·h−1). The remarkable disparity in the photocatalytic performance can be primarily ascribed to alterations in the band structure of the polymers, which includes its more stable benzene units, fluffier structure, larger specific surface area, most pronounced absorption occurring in the visible region and highly extended conjugation with a high density of electrons. The ΔEST values for PhIN-CPP and ThIN-CPP were calculated as 0.79 eV and 0.80 eV, respectively, based on DFT and TD-DFT calculations, which revealed that the incorporation of triazine units in the as-prepared CMPs could enhance the charge transfer via S1 ↔ T1 and was beneficial to the photocatalytic decomposition of H2O. This study presents a novel concept for developing a hybrid system for preparation of H2 by photocatalysis with effectiveness, sustainability, and economy.