Confined Heterojunction in Hollow-Structured TiO and Its Directed Effect in Photodriven Seawater Splitting.

The high salinity of seawater often strongly affects the activity and stability of photocatalysts utilized for photodriven seawater splitting. The current investigation is focused on the photocatalyst H-TiO/CuO, comprised of hydroxyl-enriched hollow mesoporous TiO microspheres containing incorporated CuO nanoparticles. The design of H-TiO/CuO is based on the hypothesis that the respective hollow and mesoporous structure and hydrophilic surfaces of TiO microspheres would stabilize CuO nanoparticles in seawater and provide efficient and selective proton adsorption. H-TiO/CuO shows hydrogen production performances of 45.7 mmol/(g·h) in simulated seawater and 17.9 mmol/(g·h) in natural seawater, respectively. An apparent quantum yield (AQY) in hydrogen production of 18.8% in water (and 14.9% in natural seawater) was obtained at 365 nm. Moreover, H-TiO/CuO displays high stability and can maintain more than 90% hydrogen evolution activity in natural seawater for 30 h. A direct mass- and energy- transfer mechanism is proposed to clarify the superior performance of H-TiO/CuO in seawater splitting.