Two New Armtype Polyoxometalates Grafted on Titanium Dioxide Films: Towards Enhanced Photoelectrochemical Performance.

Two new carboxyethyltin-functionalized polyoxometalates (POMs) were successfully obtained and confirmed with physicochemical and spectroscopic methods including X-ray crystallography. The lowest unoccupied molecular orbitals of both compounds are higher in energy than that of TiO2 , and the optical band gaps of these compounds are smaller than that of TiO2 . Grafting them onto a TiO2 film created two kinds of novel photoanode materials that showed significantly enhanced photovoltaic and photocurrent responses, as well as improved photoelectrooxidation activities for methanol relative to that shown by a single TiO2 film. Further, P2 W15 -Co-SnR produced the largest photocurrent by exploring the photoelectric activities of a series of carboxyethyltin POM derivatives. This work provides new insight into the photoelectrochemical functionalization of POM-based organic-inorganic hybrids.