Enhancing Hydrogen Generation Through Nanoconfinement of Sensitizers and Catalysts in a Homogeneous Supramolecular Organic Framework.

Enrichment of molecular photosensitizers and catalysts in a confined nanospace is conducive for photocatalytic reactions due to improved photoexcited electron transfer from photosensitizers to catalysts. Herein, the self-assembly of a highly stable 3D supramolecular organic framework from a rigid bipyridine-derived tetrahedral monomer and cucurbit[8]uril in water, and its efficient and simultaneous intake of both [Ru(bpy)3 ]2+ -based photosensitizers and various polyoxometalates, that can take place at very low loading, are reported. The enrichment substantially increases the apparent concentration of both photosensitizer and catalyst in the interior of the framework, which leads to a recyclable, homogeneous, visible light-driven photocatalytic system with 110-fold increase of the turnover number for the hydrogen evolution reaction.