Simple Functionalization of a Donor Monomer to Enhance Charge Transfer in Porous Polymer Networks for Photocatalytic Hydrogen Evolution

Porous polymer networks (PPNs) are promising candidates as photocatalysts for hydrogen production. Constructing a donor‐acceptor structure is known to be an effective approach for improving photocatalytic activity. However, the process of how a functional group of a monomer can ensure photoexcited charges transfer and improve the hydrogen evolution rate (HER) has not yet been studied on the molecular level. Herein, we design and synthesize two kinds of triazatruxene (TAT)‐based PPNs: TATR‐PPN with a hexyl (R) group and TAT‐PPN without the hexyl group, to understand the relationship between the presence of the functional group and charge transfer. The hexyl group on the TAT unit was found to ensure the transfer of photoexcited electrons from a donor unit to an acceptor unit and endowed the TATR‐PPN with stable hydrogen production. Triazatruxene (TAT)‐based PPNs were synthesized to investigate how the existence of a hexyl functional group would affect charge transfer. The hexyl group on the TAT unit ensured the transfer of photoexcited electrons from a donor unit to an acceptor unit, resulting in improved photocatalytic activity and hydrogen production.