Encapsulated Triplet-Triplet Annihilation-Based Upconversion in the Aqueous Phase for Sub-Band-Gap Semiconductor Photocatalysis

We herein report the first instance of aqueous-phase photosensitization of semiconductor photocatalysts (WO3 loaded with Pt) through triplet-triplet annihilation (TTA)-based upconversion of sub-band-gap photons. The TTA-based upconversion (UC) was achieved in the aqueous phase by encapsulating the solvent phase containing a benchmark platinum(II) octaethylporphyrin/9,10-diphenylanthracene sensitizer/acceptor pair in a rigid polymer shell in the form of aqueous dispersible microcapsules. A mixture of hexadecane and polyisobutylene,was used as the inner solvent phase. This eliminated the need for the deoxygenation step that is essential for existing TTA-based UC processes and enabled stable UC to occur even after a month of exposure to the ambient environment. The photo-luminescence properties were examined, and UC-assisted photochemical production of hydroxyl radical from green (532 nm) light irradiation was demonstrated for the first time.