Dual Regulation of Charge Dynamics and Active Sites in Conjugated Porous Polymers for Efficient Photocatalytic H₂ Production

Unfortunately, most D-A-type polymeric photocatalysts still suffer from sluggish charge dynamics and deficient active sites. Herein, two organic porous polymers with different molecular structures are reported using triazine ring (Tz, A₁) and dithieno[3,2-b:2′,3′-<i>d</i>]thiophene-S,S-dioxide (DTDO, A₂) as acceptors.

Compared to TPH-DTDO with the D-A structure, TTZ-DTDO possesses an extra charge transfer channel, more active sites, and stronger charge separation ability due to its A₁-D-A₂ structure, achieving the dual regulation of charge dynamics and active sites. These advantages enable TTZ-DTDO to realize an excellent H₂ generation rate of 21.15 mmol h⁻¹ g⁻¹ under full arc light (320 nm < λ < 780 nm), which is approximately 5.5 times higher than that of TPH-DTDO (3.83 mmol h⁻¹ g⁻¹), demonstrating the positive influence of the A₁-D-A₂ molecular design on upgrading the photocatalytic efficiency of organic polymers.