A hydrazone-based covalent organic framework for photocatalytic hydrogen production

Covalent organic frameworks (COFs) have recently emerged as a new generation of porous polymers combining molecular functionality with the robustness and structural definition of crystalline solids. Drawing on the recent development of tailor-made semiconducting COFs, we report here on a new COF capable of visible-light driven hydrogen generation in the presence of Pt as a proton reduction catalyst (PRC). The COF is based on hydrazone-linked functionalized triazine and phenyl building blocks and adopts a layered structure with a honeycomb-type lattice featuring mesopores of 3.8 nm and the highest surface area among all hydrazone-based COFs reported to date. When illuminated with visible light, the Pt-doped COF continuously produces hydrogen from water without signs of degradation. With their precise molecular organization and modular structure combined with high porosity, photoactive COFs represent well-defined model systems to study and adjust the molecular entities central to the photocatalytic process.