Covalent graft of Polypyridineruthenium(II) Complex-ZnTPP dyad with fullerol and immobilization onto TiO2 for enhanced photoassisted water oxidation activity

Abstract

The covalent linkage of the light-harvester with the water oxidation catalyst is an effective way to construct heterogeneous catalysts with both light harvesting ability and catalytic oxygen evolution activity, and remains a challenge for simulated photosynthesis systems. Herein, two heterogeneous composite catalysts of ZnTPPtpyRubpyPHFTiO2 and ZnTPPtpyRubpyTiO2, with both the light harvesting capability and the catalytic water oxidation (CWE) performance, were successfully designed and prepared, and were fully characterized. Research indicated that the transfer mode of the photo-generated carrier for the two photo-assisted heterogeneous catalysts follows the type II mechanism, and the photo-generated holes promote the CWE activity. Compared to the dark condition (with TOF values of 42.3 and 41.8, respectively), ZnTPPtpyRubpyPHFTiO2 and ZnTPPtpyRubpyTiO2 exhibit superior CWE activity and efficiency in the illumination condition (with TOF values of 120 and 48.31, respectively). Fullerol, playing the role of an electron acceptor and an electron-pool, promotes charge separation and electron storage, which leads to a better suppression in charge recombination and enhancement in charge injection for ZnTPPtpyRubpyPHFTiO2. Therefore, ZnTPPtpyRubpyPHFTiO2 demonstrates a significantly improved catalytic activity in the illumination condition with a much higher TOF value compared to that of ZnTPPtpyRubpyTiO2.