Stabilisation of molecular TiO4 species on the pore surface of mesoporous silica for photocatalytic H2 evolution.

Although molecular tetrahedral Ti-oxo species exhibit unique electronic and photochemical properties due to their discrete energy levels, which are different from those of anatase and rutile, such Ti-oxo species are generally unstable and readily transformed to amorphous/crystalline TiO2 (bulk phases, nanoparticles and clusters) via hydrolysis and condensation. Here, molecular Ti-oxo species were immobilised within mesoporous silica SBA-15 by grafting titanium(IV) oxyacetylacetonate using the surface silanol groups of SBA-15 as a scaffold, followed by chemical etching with dilute hydrochloric acid to form molecular TiO4 species. These Ti species mainly exist as isolated tetrahedrally coordinated structures, as was confirmed by diffuse reflectance UV-vis and Raman spectroscopy. The SBA-15-immobilised molecular TiO4 exhibited higher photocatalytic activity for H2 evolution from an aqueous methanol solution than conventional Ti-incorporated mesoporous silica (Ti-MCM-41) and reference TiO2 (P25).