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 here report on a new COF, TFPT-COF, capable of visible-light driven hydrogen generation in the presence of Pt as proton reduction catalyst (PRC) with quantum efficiencies of up to 2.2%. The COF is based on hydrazone-linked functionalized triazine 1,3,5-tris-(4-formyl-phenyl)triazine (TFPT) 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 of 2177 m2/g among all hydrazone-based COFs reported to date.When illuminated with visible light, the Pt-doped COF continuously produces hydrogen from water in the presence of ascorbic acid as sacrificial electron donor without signs of degradation. While amorphization is observed during the photocatalytic process, facile recrystallization without significant loss in porosity was achieved by subjecting the COF to the original synthesis conditions.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 photocatalyic process.

TFPT-COF: A hydrazone-based covalent organic framework as a platform for solar energy conversion

248th National Meeting (2014)

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