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Pachfule, Pradip; Acharjya, Amitava; Roeser, Jérôme; Langenhahn, Thomas; Schwarze, Michael; Schomäcker, Reinhard; Thomas, Arne; Schmidt, Johannes
Journal of the American Chemical Society, 01/2018, Volume: 140, Issue: 4Journal Article
Covalent organic frameworks (COFs) are crystalline, highly porous, two- or three-dimensional polymers with tunable topology and functionalities. Because of their higher chemical stabilities in comparison to their boron-linked counterparts, imine or β-ketoenamine linked COFs have been utilized for a broad range of applications, including gas storage, heterogeneous catalysis, energy storage devices, or proton-conductive membranes. Herein, we report the synthesis of highly porous and chemically stable acetylene (−CC−) and diacetylene (−CC–CC−) functionalized β-ketoenamine COFs, which have been applied as photocatalyst for hydrogen generation from water. It is shown that the diacetylene moieties have a profound effect as the diacetylene-based COF largely outperforms the acetylene-based COF in terms of photocatalytic activity. As a combined effect of high porosity, easily accessible diacetylene (−CC–CC−) functionalities and considerable chemical stability, an efficient and recyclable heterogeneous photocatalytic hydrogen generation is achieved.
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